KR102409503B1 - Photoactive devices and materials - Google Patents

Abstract

Disclosed herein is a deposition method for depositing a thin film comprising a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase on a substrate in a reaction space. The deposition method may include a plurality of super-cycles. Each super-cycle may include a dielectric transition metal compound sub-cycle and a reducing sub-cycle. The dielectric transition metal compound sub-cycle includes contacting the substrate with a dielectric transition metal compound. The reducing sub-cycle includes alternatingly and sequentially contacting the substrate with a reducing agent and a nitrogen reactant. The thin film includes a dielectric transition metal compound phase included on a conductive or semiconducting transition metal compound.

Description

Photoactive devices and materials

The present application relates to the field of photoactive devices and materials, and more particularly, to a method for forming a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase.

Atomic layer deposition (ALD) is based on sequential, self-saturating surface reactions that can provide good conformality and step coverage regardless of the geometry of the structure to be coated. However, deposition of metal films by ALD has been challenging, in part because ALD is inherently based on thermodynamically favored half-reactions.

Refractory metal conductive layers are fundamental building blocks in micro and nanoelectronics. Oxidation-resistant metal films are desirable in many situations. For example, titanium nitride layers are commonly used in the semiconductor manufacturing industry, for example as gate electrode materials or copper diffusion barriers. However, it is known that titanium nitride is oxidized to a depth of several tens of nanometers, possibly through grain boundaries, when placed in air.

In addition, photoactive materials and/or electrically conductive, transmissive materials are useful in a variety of situations. For example, photoactive materials can be used to convert the radiant energy of photons into electrical energy, which is an important factor in, for example, solar cells.

In some embodiments, an atomic layer deposition (ALD) method for depositing a thin film comprising a dielectric transition metal compound phase comprised on a conductive or semiconducting transition metal compound is provided. In some embodiments, the dielectric transition metal compound phase may include a transition metal oxide or a transition metal fluoride. In some embodiments, the dielectric transition metal compound phase may include TiF ₃ . In some embodiments, the conductive or semiconducting phase can include a transition metal element, a transition metal alloy, a transition metal oxide, a transition metal nitride, a transition metal silicide, and/or a transition metal carbide. In some embodiments, the conductive or semiconducting transition metal compound phase may be TiN. In some embodiments, the dielectric transition metal compound phase may be TiF ₃ , and the conductive or semiconducting transition metal compound phase may be TiN.

In some embodiments, the dielectric transition metal compound phase may include discrete particles. In some embodiments, the dielectric transition metal compound phase may include particles having a diameter ranging from about 0.1 nm to about 500 nm. In some embodiments, the dielectric transition metal compound phase surrounds the dielectric transition metal compound phase particles.

In some aspects, an atomic layer deposition (ALD) method is provided for depositing a thin film on a substrate comprising a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase in a reaction space. In some implementations, the ALD method can include a plurality of super-cycles, wherein at least one super-cycle includes two sub-cycles: a metal fluoride sub-cycle and a second sub-cycle. . In some implementations, the metal fluoride sub-cycle comprises contacting a substrate with a metal fluoride, wherein the second sub-cycle alternates the substrate with a silane or borane and a nitrogen reactant and sequentially contacting them. In some embodiments, the second sub-cycle is referred to as a reducing sub-cycle, and the substrate is contacted with a reducing agent and a nitrogen reactant. In some implementations, the substrate may include silicon.

According to some embodiments, the transition metal of the dielectric transition metal compound includes a metal selected from Ti, Ta, Nb, Mo, and W. In some embodiments, the dielectric transition metal compound includes a transition metal fluoride. In some embodiments, the transition metal fluoride includes TiF ₄ . In some embodiments, the reducing agent is a silane or borane. In some embodiments, the reducing agent comprises disilane or trisilane. In some embodiments, the reducing agent comprises diborane or triborane. In some embodiments, the nitrogen reactant is selected from ammonia, N ₂ H ₄ , a nitrogen atom, a nitrogen containing plasma, and a nitrogen radical. In some embodiments, the transition metal fluoride is TiF ₄ and the reducing agent is Si ₃ H ₈ . In some embodiments, the metal fluoride sub-cycle and the reducing sub-cycle are performed in at least one of the plurality of super-cycles in a ratio of at least about 0.1. In some embodiments, the thin film comprises TiF ₃ .

According to some embodiments, a thin film comprising a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase is from about 0.1 to about 10 at%, from about 0.1 to about 5 at%, or from about 0.4 to about 2.3 at% silicon includes In some embodiments, the thin film comprises from about 1 to about 50 at% nitrogen, from about 5 to about 45 at% nitrogen, from about 10 to about 50 at% nitrogen. In some embodiments, the thin film is conductive. In some embodiments, the thin film has a layer resistivity of about 10 ⁷ μΩcm. In some embodiments, the thin film has a layer resistivity of about 500 μΩcm to about 5Х10 ⁶ μΩcm. In some embodiments, the thin film has a layer resistivity of about 5Х10 ³ μΩcm to about 5Х10 ⁶ μΩcm. In some embodiments, the thin film has a layer resistivity of about 10 ⁴ μΩcm to about 10 ⁶ μΩcm. In some embodiments, the thin film is not oxidized by ambient air below about 300 °C.

In some embodiments, the thin film comprises a mixture of a dielectric transition metal compound and a conductive or semiconducting transition metal compound. In some embodiments, the thin film comprises a dielectric transition metal compound phase incorporated on a conductive or semiconducting transition metal compound. In some embodiments, the thin film comprises TiF ₃ and TiN.

In some embodiments, the thin film is a photoactive material configured to absorb the radiant energy of one or more photons to generate electrical energy. In some embodiments, the thin film is transparent or partially transparent. In some embodiments, the thin film is electrically conductive. In some embodiments, the membrane comprises a waveguide configured to guide the propagation of an electromagnetic wave.

In some embodiments, the thin film is configured to absorb at least a portion of light incident on the composite thin film to create a potential difference within the composite thin film. In some embodiments, the thin film is electrically conductive and transparent to light, and at least a portion of the light incident on the thin film surface passes through the thin film. In some embodiments, the thin film is configured to transmit information contained in a modulated light beam incident on a surface of the thin film as an electromagnetic wave within the thin film.

According to some embodiments, a thin film including TiF ₃ included on TiN is disclosed herein. In some embodiments, the thin film comprises from about 5 to about 50 at% nitrogen. In some embodiments, the thin film comprises from about 0.4 to about 2.3 at% silicon. In some embodiments, the thin film has a thickness of less than about 100 nm. In some embodiments, the thin film has a thickness of less than about 10 nm. In some embodiments, the thin film can have a thickness of up to about 100 nm, about 1 μm, or in some instances about 1 mm.

In some embodiments, the thin film comprises a mixture of a dielectric transition metal compound and a conductive or semiconducting transition metal compound. In some embodiments, the thin film comprises a dielectric transition metal compound phase incorporated on a conductive or semiconducting transition metal compound. In some embodiments, the thin film comprises TiF ₃ and TiN. In some embodiments, the thin film is a photoactive material configured to absorb the radiant energy of one or more photons to generate electrical energy in an electrical circuit. In some embodiments, the thin film is photon transmissive or partially photon transmissive. In some embodiments, the composite thin film is electrically conductive. In some embodiments, the membrane comprises a waveguide configured to guide the propagation of an electromagnetic wave.

In some embodiments, the thin film is configured to absorb at least a portion of light incident on the thin film to create a potential difference within the composite thin film. In some embodiments, the thin film is electrically conductive and transparent to light, and at least a portion of the light incident on the thin film surface passes through the thin film. In some embodiments, the thin film is configured to transmit information contained in a modulated light beam incident on a surface of the thin film as an electromagnetic wave within the thin film.

According to some embodiments, disclosed herein is an optical device comprising a dielectric transition metal compound phase incorporated on a conductive or semiconducting transition metal compound. As used herein, the term photonic device may refer to a component or device capable of generating, detecting, absorbing, processing, or reacting to a photon, ie, light. The term optical device may refer to, for example, a laser diode, a light emitting diode, a solar cell, and/or photovoltaic cells. In some embodiments, the dielectric transition metal compound phase may include discrete particles. In some embodiments, the dielectric transition metal compound phase may include particles of about 0.1 nm to about 500 nm. In some embodiments, the dielectric transition metal compound phase surrounds the dielectric transition metal compound phase particles.

In some embodiments, the optical device comprises a photoactive component, such as a photoelectrode. In some embodiments, the photoactive component is configured to absorb radiant energy of photons to generate electrical energy in the circuit. In some embodiments, the photoactive component is configured to generate photons with electrical energy. In some embodiments, the photoactive component comprises a dielectric transition metal compound phase incorporated on a conductive or semiconducting transition metal compound. In some embodiments, the photoactive component comprises a conductive material. In some embodiments, the photoactive component comprises Si, SiGe, Ge, CdTe, GaAs, GaSb and/or InGaAs. In some embodiments, the photoactive component comprises TiF ₃ and TiN.

In some implementations, the optical device includes a photon transmissive component, the photon transmissive component configured to allow photons to pass through the photon transmissive component. In some embodiments, the photon transmissive component comprises a dielectric transition metal compound phase incorporated on a conductive or semiconducting transition metal compound. In some embodiments, the photon transmissive component comprises TiF ₃ and TiN.

In some embodiments, the photonic device includes a charge collection component configured to collect photon-excited charge carriers. In some embodiments, the charge collection component comprises a dielectric transition metal compound phase incorporated on a conductive or semiconducting transition metal compound. In some embodiments, the charge collection component comprises indium tin oxide, doped tin oxide, zinc oxide, doped zinc oxide, conductive polymer, metal grid, carbon nanotube, graphene, or nanowire thin film. In some embodiments, the photon transmissive component comprises TiF ₃ and TiN.

In some implementations, the optical device includes a waveguide component configured to convey a characteristic of a photon flux incident on at least a portion of the optical device. In some embodiments, the waveguide component comprises a dielectric transition metal compound phase incorporated on a conductive or semiconducting transition metal compound.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be better understood from the detailed description and accompanying drawings, which are meant to illustrate the invention and do not limit the invention, of which:
1 is a flow diagram illustrating an ALD method for depositing a thin film comprising a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase in accordance with some embodiments.
2 is TiF ₃ /TiN according to an embodiment A flowchart illustrating an ALD method for depositing a film.
3 shows an XRD pattern of a film formed according to an embodiment of the present disclosure.
4 is an analysis of the oxidation behavior of a film formed according to an embodiment of the present disclosure.
5 is a further analysis of the oxidation behavior of a film formed according to an embodiment of the present disclosure.
6 shows a dark field TEM image and a cross-sectional TEM image of a TiN film deposited using TiF ₃ particles contained therein and TiF ₄ , Si ₂ H ₆ as a reducing agent and NH ₃ as a nitrogen reactant. .
7A and 7B show bright field and dark field TEM images of a TiN film including TiF ₃ particles contained therein.
₈ is an energy _dispersive X _{- ray spectroscopy} ( EDS) is shown.
FIG. 9 shows the XPS depth profile of a sample TiN film deposited using TiF ₃ particles included therein, TiF ₄ , Si ₂ H ₆ as a reducing agent, and NH ₃ as a nitrogen reactant.
10a and 10b show a dark field TEM image and a cross-sectional TEM image of a TiN film deposited using TiF ₄ , Si ₃ H ₈ as a reducing agent, and NH ₃ as a nitrogen reactant, including TiF ₃ particles contained therein.
11 shows EDS images of element distributions in a sample TiN film deposited using TiF ₃ particles included therein, TiF ₄ , Si ₃ H ₈ as a reducing agent, and NH ₃ as a nitrogen reactant.
12 shows an XRD pattern of a sample TiN film deposited using TiF ₃ particles included therein, TiF ₄ , Si ₃ H ₈ as a reducing agent, and NH ₃ as a nitrogen reactant.
13 shows an XPS depth profile for a sample TiN film deposited using TiF ₃ particles included therein, TiF ₄ , Si ₃ H ₈ as a reducing agent, and NH ₃ as a nitrogen reactant.
14a and 14b are schematic diagrams of photoelectric analysis of sample TiN films deposited with TiF ₃ particles contained therein and using TiF ₄ , Si ₂ H ₆ /Si ₃ H ₈ as a reducing agent and NH ₃ as a nitrogen reactant. show
15A and 15B show schematic diagrams of photovoltaic cells having a top electrode deposited therein with TiF ₃ particles contained therein and using TiF ₄ , Si ₂ H ₆ /Si ₃ H ₈ as a reducing agent and NH ₃ as a nitrogen reactant. .

Thin films comprising a dielectric transition metal compound phase, such as a metal fluoride or metal oxide phase, incorporated within a conductive or semiconducting transition metal compound phase may have photoactive properties. For example, the resistance of these composite films may change upon exposure to light. In some embodiments, such composite films may include discrete particles on a dielectric transition metal compound incorporated on a conductive or semiconducting transition metal compound. In some embodiments, the dielectric transition metal compound phase may include particles having a diameter ranging from about 0.1 nm to about 500 nm. In some embodiments, the dielectric transition metal compound phase surrounds the dielectric transition metal compound phase particles. For example, in some embodiments, the composite film may include discrete TiF ₃ particles included in TiN. In some embodiments, the dielectric transition metal compound phase may include an oxide or a fluoride. In some embodiments, the dielectric transition metal compound includes a transition metal oxide, a transition metal fluoride, a transition metal oxyfluoride, or a mixture of one or more thereof. In some embodiments, the dielectric transition metal compound is composed of a transition metal oxide, a transition metal fluoride, a transition metal oxyfluoride, or a mixture of one or more thereof. In some embodiments, the dielectric transition metal compound phase may be selected from the group consisting of: TiF ₃ , Cr ₂ O ₃ , NiO, WO ₃ , Ti ₂ O ₃ , TiOF ₂ , NbO ₂ F, NbO _{3 - x} F _x , NbO _{x /2} F _3-x , MoO _{3 - x} F _x , MoO _x F _{3 -x} , TaO ₂ F, TaO _x F _{3 -x} , WO _{3- x} F _x . In some embodiments, the dielectric transition metal compound phase may include: TiF ₃ , Cr ₂ O ₃ , NiO, WO ₃ , Ti ₂ O ₃ , TiOF ₂ , NbO ₂ F, NbO _{3 - x} F _x , NbO _{x /2} F _{3-x ,} MoO _{3 -x} F _x , MoO _x F _{3 -x} , TaO ₂ F, TaO _x F _{3 -x} , or WO _{3- x} F _x , or mixtures of one or more thereof. In some embodiments, the dielectric transition metal compound phase has a ReO ₃ similar structure. In some embodiments, the dielectric transition metal compound phase includes a crystal structure similar to that of ReO ₃ . The term ReO ₃ like structure is not intended to limit the dielectric transition metal compound phase to ReO ₃ , it is simply to suggest that the dielectric transition metal compound phase may include a crystal structure similar to that of ReO ₃ (rhenium (IV) oxide). used to illustrate. The exemplary ReO ₃ like structure can also be thought of as a perovskite (ABO ₃ )-type crystal structure in which a large A cation is lost in the center of the unit cell. The ReO ₃ like structure is a cubic structure with a metal atom at each corner of the unit cell and one nonmetal atom such as oxygen or fluorine at each unit cell edge, roughly in the middle between the metal atoms. In some embodiments, the ReO ₃ like structure comprises a modified structure from an ideal ReO 3 like structure. In some embodiments, the dielectric transition metal compound comprises a Pm3m {221} space group such as a ReO ₃ like structure.

In some embodiments, the conductive or semiconducting transition metal compound phase is a metal element such as a transition metal, a metal alloy such as a metal alloy containing a transition metal, a metal nitride such as a transition metal nitride, a metal carbide such as a transition metal carbide, or It may include mixtures of two or more of these. In some embodiments, the conductive or semiconducting transition metal compound phase is a metal element such as a transition metal, a metal alloy such as a metal alloy containing a transition metal, a metal nitride such as a transition metal nitride, a metal carbide such as a transition metal carbide, or It may be selected from the group consisting of mixtures of two or more of these. In some embodiments, the conductive or semiconducting transition metal compound phase can include a Period 4 element of the Periodic Table of the Elements. In some embodiments, the conductive or semiconducting transition metal compound phase can be selected from the group consisting of Cr, TiN, Fe, W, TiC, Ti, or a mixture of one or more thereof. In some embodiments, the conductive or semiconducting transition metal compound phase may be selected from the group consisting of Cr, TiN, Fe, W, TiC or Ti, or a mixture of one or more thereof.

Thin films comprising a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase disclosed herein can be used in a variety of situations. For example, a conductive film containing a metal fluoride such as a conductive fluoride film or a conductive thin film containing TiF ₃ may be used as the oxygen barrier film on the TiN layer or other metal film. In some embodiments, conductive fluoride containing films formed in accordance with the present disclosure will be useful as a barrier film against ashing or other oxidizing conditions. In some embodiments, conductive fluoride-containing films formed in accordance with the present disclosure can be used as a protective layer against an ambient environment containing oxygen and/or water or moisture, such as ambient air. In some implementations, the fluoride containing films of the present disclosure are useful as a sacrificial layer, for example, in a patterning layer or in other applications where good oxidation resistance is desired. In some implementations, the conductive fluoride film is conformally deposited on vertical and horizontal surfaces. In some implementations, the conductive film comprising metal fluoride is p-type over the gate stack, eg, on top of a high-k layer, such as HfO ₂ , and below the actual gate electrode layer or conductive gate dielectric barrier layer. It can be used as a capping layer. In some embodiments, when a conductive film comprising metal fluoride is used as the p-type capping layer, the effective workfunction of the electrode in this laminate is greater than about 4.9 eV, preferably from about 5.0 to about 5.2 eV.

Thin films comprising a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase may be used in various situations, such as as photoactive materials. In some implementations, thin films formed according to the present disclosure can be used as a photoelectrode of a photoactive device. In some implementations, the thin film can absorb the radiant energy of photons that generate electrical energy in the circuit. In some implementations, the thin film is deposited on a substrate comprising silicon. In some implementations, the thin film is deposited on a substrate comprising glass, quartz, and/or SiO ₂ . In some implementations, the substrate can include a silicon wafer or a portion thereof. In some embodiments, as will be apparent to those skilled in the art, the thin film is deposited on a typical substrate used, for example, in thin film solar cell fabrication.

In some implementations, the thin film of the present disclosure may be used as a photon transmissive component of a photoactive device. In some implementations, the thin film of the present disclosure can be used as a charge collection component of a photoactive device. In some implementations, the thin film of the present disclosure can be used as a waveguide component of a photoactive device. In some embodiments, a film comprising a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase does not include one or more of the following materials: MgF ₂ , CaF ₂ , ZnF ₂ , SrF ₂ , YF ₃ , or LaF ₃ . In some embodiments, the film does not include one or more of the following materials: AlF ₃ or LiF. In some embodiments, the film does not include one or more of the following materials: an alkali metal fluoride (Group 1 of the Periodic Table of the Elements) such as KF or an alkaline earth (Group 2 of the Periodic Table of the Elements) metal such as MgF ₂ or CaF ₂ fluoride. In some embodiments, the thin film does not include one or more of the following materials: Group III fluorides such as YF ₃ or LaF ₃ . In some embodiments, the film contains greater than about 20 at%, preferably no more than about 10 at%, more preferably no more than 5 at%, and most preferably no more than 1 at% of one or more of the following materials: Does not contain: alkali metals, alkaline earth metals, and Group 3 metals. In some embodiments, the film contains greater than about 20 at%, preferably no more than about 10 at%, more preferably no more than 5 at%, and most preferably no more than 1 at% of one or more of the following materials: Does not contain: Mg, Ca, Zn, Sr, Y, or La. In some embodiments, the film has greater than about 20 at%, preferably no more than about 10 at%, more preferably no more than 5 at%, and most preferably no more than 1 at% of metals excluding one or more of the following materials: at % or less: Ti, Zr, Hf, V, Nb, Ta, Cr, Ni, Fe, Mo, or W, and preferably any metal other than one or more of the following metals: Ti, Nb, Ta , Mo, and W. As discussed herein, thin films comprising a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase may be deposited by vapor deposition methods, such as atomic layer deposition (ALD). Such films may preferably be oxidation resistant, conductive, photoactive, and/or photon transmissive. In some embodiments, the thin film may include titanium fluoride (TiF ₃ ). TiF ₃ is a stable solid fluoride that can be used in a variety of situations, such as materials forming catalysts, photoactive materials, photoelectrodes, waveguides, charge collection components, and/or photon transmissive materials.

The presence of fluorine in some metal films improves oxidation resistance. Metal nitrides such as titanium nitride are commonly used in the semiconductor industry, for example as barrier films. However, as discussed above, titanium nitride films can undergo unwanted oxidation. This application is based, in part, on the unexpected discovery that conductive thin films comprising metal fluoride can be deposited, such as conductive thin films comprising titanium fluoride. In some implementations, the titanium fluoride containing film has greater oxidation resistance than a TiN film, eg, a TiN film deposited by known vapor deposition methods such as ALD and/or CVD.

In some embodiments, vapor deposition methods are provided for depositing a thin film comprising a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase. In some embodiments, the deposition method for depositing a thin film comprising a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase on a substrate is an atomic layer deposition (ALD) type method, a chemical vapor deposition (CVD) type method. method, or a combination method of ALD and CVD. In some implementations, other methods may be used, such as physical vapor deposition (PVD), plasma enhanced atomic layer deposition (PEALD), and the like.

In some embodiments, the methods can include a first sub-cycle in which the substrate is exposed to a vapor phase dielectric transition metal compound, such as TiF ₄ , and a monolayer of the dielectric transition metal compound is adsorbed onto the substrate surface. In a second sub-cycle, a gaseous silane or borane compound, or other “reducing agent,” and a gaseous nitrogen reactant are provided alternately, sequentially. The reducing agent and nitrogen reactant react with the dielectric transition metal compound on the substrate surface to form a film comprising a fluoride precursor transition metal compound phase and a conductive or semiconducting transition metal compound phase. In some embodiments, the first sub-cycle may include both a gaseous dielectric transition metal compound such as TiF ₄ and a reducing agent such as silane or borane. In some embodiments, the second cycle does not include silane or borane. Accordingly, in some embodiments, the first cycle comprises a gaseous dielectric transition metal compound and a silane or borane, and the second cycle comprises a gaseous nitrogen reactant. Although the term “reducing agent” is used, in some embodiments, chemical reduction is not required. Thus, in some embodiments, "reducing agent" refers only to a silane compound or a borane compound. However, without wishing to be bound by any theory, it is believed that, in some embodiments, the reducing agent could reduce the oxidative state of the metal species on the substrate, as discussed herein.

In some implementations, the metal may be selected from, for example, Tin, Ta, Nb, Mo, and W. The reducing agent may be, for example, a silane or borane compound. The nitrogen reactant may be, for example, NH ₃ . In some embodiments where a nitrogen reactant is used, the nitrogen reactant may exhibit at least some reducing effect on the oxidation state of the metal species on the substrate surface.

The first and second sub-cycles together constitute an ALD super-cycle. In each super-cycle, the first sub-cycle and the second sub-cycle may independently be repeated one or more times. In addition, the super-cycle may be repeated one or more times to deposit a conductive film comprising a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase to a desired thickness. The first and second sub-cycles may be performed in any order. For example, in some implementations, the second sub-cycle may be performed first. In addition, the order of the reactants in each sub-cycle may vary. For example, in some embodiments, in a reducing sub-cycle, which may be performed first or second, the nitrogen reactant is pulsed in front of a silane or borane compound and vice versa.

In one or more super-cycles, the ratio of the first sub-cycle to the second sub-cycle may be varied to deposit a film having a desired composition and/or desired properties. In some implementations, the ratio of the first sub-cycle to the second sub-cycle is the same in each super-cycle of the ALD method. In some implementations, the ratio of the first sub-cycle to the second sub-cycle can be varied in one or more super-cycles during the deposition method.

In some embodiments, a conductive film is formed comprising a fluoride dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase, the film comprising some silicon or boron obtained from a reducing compound and/or obtained from a nitrogen reactant Contains some nitrogen. For example, in some embodiments, a conductive thin film comprising TiF ₃ is deposited, which thin film contains some Si and some N.

All atomic fraction (ie, at %) values presented herein exclude hydrogen for the sake of simplicity, since it is difficult to accurately quantitatively analyze hydrogen. However, in some embodiments, the hydrogen content of the membranes is inversely less than 20 at%, less than about 10 at%, or less than about 5 at%, if it is possible to analyze hydrogen with significant accuracy.

In some embodiments, silane is used as the reducing agent, and the conductive film comprising the fluoride dielectric transition metal compound phase and the conductive or semiconducting transition metal compound phase also includes a small amount of silicon. For example, in some embodiments, the silicon content can be less than about 15 at%. In some embodiments, the silicon content can be from about 0.01 to about 10 at%, from about 0.1 to about 5 at%, or from about 0.1 to about 2 at%. In some embodiments, the silicon content in the conductive film comprising metal fluoride is preferably less than about 1.5 at%.

In some embodiments, borane is used as the reducing agent, and the conductive film comprising the fluoride dielectric transition metal compound phase and the conductive or semiconducting transition metal compound phase also includes a small amount of boron. For example, in some embodiments, the boron content can be less than about 15 at%. In some embodiments, the boron content is from about 0.01 to about 10 at%, from about 0.1 to about 5 at%, or from about 0.1 to about 2 at%. In some embodiments, the boron content is less than about 1.5 at%.

In some embodiments, the films contain a small amount of nitrogen. For example, in some embodiments, the nitrogen content can range from about 0.5 to about 50 at%, from about 1 to about 20 at%, or from about 2 to about 15 at%.

In some embodiments, the films include fluorine in an amount greater than about 10 at%, from about 20 to about 75 at%, from about 40 to about 70 at%, or from about 45 to about 65 at%.

In some embodiments, the films have a fluorine to titanium ratio (F/Ti (at%/at%)) of about 0.25 to about 5, about 0.5 to about 3, or about 1 to about 2.5.

In some implementations, despite the fact that the films are oxidation resistant, the films may contain a small amount of oxygen. For example, in some embodiments, the oxygen content is less than about 2.5 at%, less than about 1.5 at%, less than about 1.0 at%, or even less than about 0.5 at%.

In some embodiments, a thin film deposited by an ALD method described herein comprising a fluoride dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase is formed by a known vapor deposition method, such as a corresponding metal deposited by ALD. It has greater oxidation resistance than nitride films. In some embodiments, the thin film deposited by the ALD method described herein is a photoactive material.

In some implementations, the thin films absorb some of the light incident on the surface of the film, creating a potential difference in the film or current flow in the film. In some embodiments, the thin film is light transmissive or photon transmissive, ie, the thin film allows at least some of the light incident on the surface of the membrane to pass through the membrane. In some embodiments, the thin film transmits information contained in a modulated light beam incident to the surface of the thin film by electromagnetic waves.

In some implementations, the conductive thin film comprising TiF ₃ undergoes a first sub-cycle for absorbing TiF ₄ in a self-limiting manner and a second sub-cycle for reducing TiF ₄ to TiF ₃ on the substrate surface. deposited by an ALD method, including For example, TiF ₄ is provided in the first sub-cycle such that TiF ₄ leading to a monolayer is formed on the substrate surface. The first sub-cycle may be repeated two or more times. In some implementations, a purge step is included between each first sub-cycle. In the second sub-cycle, the substrate is alternately and sequentially exposed to a reducing agent such as a silane or borane compound, and a nitrogen reactant such as ammonia. The second sub-cycle serves to reduce at least a portion of the TiF ₄ on the substrate surface to TiF ₃ . In some implementations, the formed films include TiF ₃ with relatively small amounts of silicon or boron and nitrogen. In some implementations, the formed films include some nitrogen in the form of TiF ₃ . In some embodiments, the film is a mixture of TiF ₃ and TiN. In some embodiments, the film comprises a dielectric transition metal compound phase comprised on a conductive or semiconducting transition metal compound, for example a TiF ₃ phase comprised on TiN. In some embodiments, the dielectric transition metal compound phase is in discrete form, such as discrete particles, and is surrounded by a conductive or semiconducting transition metal compound phase.

Each of the first and second sub-cycles may be repeated one or more times in the super-cycle. The super-cycle is repeated until a film of the desired thickness is achieved. By adjusting the ratio of the two sub-cycles in one or more super-cycles, the amount of TiF ₃ can be increased without introducing unwanted amounts of silicon or nitrogen. In particular, in some embodiments, increasing the number of second sub-cycles in which the substrate is alternately and sequentially contacted with a reducing agent and a nitrogen reactant compared to the first sub-cycle increases the amount of TiF ₄ converted to TiF ₃ this increases

In some embodiments, the reducing (second) sub-cycle may use a second compound, although other compounds may be used. In some embodiments, the silicone compound is a silane compound such as SiH ₄ , Si ₂ H ₆ , or Si ₃ H ₈ . In some embodiments, the boron compound can be used in at least one reducing sub-cycle. For example, in some embodiments, the reducing agent can be a borane compound, such as one or more of BH ₃ , B ₂ H ₆ , or triborane. It will be appreciated that other reducing agents may also be used. In some embodiments, the same reducing agent is used in each sub-cycle, while in other embodiments, different reducing agents can be used in one or more sub-cycles.

In some embodiments, the nitrogen reactant may include one or more of NH ₃ , a nitrogen atom, a nitrogen radical, a nitrogen plasma, such as another excitatory species comprising nitrogen that may be generated by a plasma, or other suitable nitrogen containing compounds. can

In some implementations, a thin film comprising TiF ₃ is deposited, which film does not contain fluorine in the film and is higher than a TiN film deposited by known vapor deposition methods, such as a TiN film deposited by ALD. It has oxidation resistance.

In some embodiments, a thin film comprising fluorine, such as a thin film of metal fluoride comprising at least some nitrogen, is deposited, which thin film is smooth and has no columnar grain structure. In some embodiments, a thin film comprising particles on a dielectric transition metal compound incorporated on a conductive or semiconducting transition metal compound is deposited. In some embodiments, the dielectric transition metal compound phase particles have distinct grain boundaries with the conductive or semiconducting transition metal compound phase. In some embodiments, the dielectric transition metal compound phase particles include discrete particles surrounded by the conductive or semiconducting transition metal compound phase. In some embodiments, the particles of the discrete transition metal compound phase may be less than about 500 nm in diameter, preferably less than about 100 nm in diameter, and more preferably less than about 20 nm in diameter. In some embodiments, the particles on the dielectric transition metal compound may have a diameter of less than about 10 nm. In some embodiments, the average distance between the dielectric transition metal compound particles is less than about 50 nm, preferably less than about 20 nm. In some embodiments, the average distance between the dielectric transition metal compound particles is about 10 nm to about 20 nm. In some embodiments, the dielectric transition metal compound particles include columnar grains. In some embodiments, the columnar grains extend substantially throughout the thickness of the deposited thin film.

In some implementations, a thin film comprising TiF ₃ having a thickness of about 500 nm or less is deposited. In some embodiments, the thin film has a thickness of less than about 100 nm, less than about 50 nm, less than about 30 nm, or less than about 10 nm. In some implementations, the thickness may be selected depending on the application of the film to be used. For example, in some implementations, the thickness of the film may be much less than the thickness described above, eg, from about 2 to about 50 Å, from about 3 to about 30 Å, and in some cases from about 5 to about 20 Å. can be Å. In some embodiments, the thin film can have a thickness greater than about 100 nm, greater than about 1 μm, or in some instances greater than about 1 mm.

Although mainly illustrated in the context of forming thin films comprising TiF ₃ , other dielectric transition metal compound films or films containing at least a portion of a dielectric transition metal compound include at least one sub-cycle in which a transition metal compound reactant is used. may be deposited using a deposition super-cycle, such as an ALD or CVD super-cycle. For example, in some implementations, a metal nitride film comprising two different metals and fluorine comprises a first sub-cycle in which the substrate is alternately and sequentially contacted with a first metal reactant and a first nitrogen reactant, and the substrate is It may be deposited by a deposition method comprising a second sub-cycle in contact with a metal fluoride and a reducing agent such as silane or borane. Exemplary methods are described, for example, in US Application Serial No. 13/802,157, which is incorporated herein by reference in its entirety.

The deposition methods described herein may be used to deposit films that may be referred to as MF films, such as films containing metal fluoride, ie films containing titanium fluoride. The stoichiometry of M and F, and thus the relative amounts, may vary. For example, the relative amounts of Ti and F in a film comprising titanium fluoride may vary. Also, as discussed above, in some implementations, the films may include two different metals. The amount of each element in this film can be adjusted, for example, by controlling the ratio of sub-cycles in the deposition method.

For example, in some implementations for forming films comprising TiF ₃ , reducing the number of reducing sub-cycles compared to titanium fluoride sub-cycles increases the amount of TiF ₃ in the film, while reducing TiF ₄ amount can be reduced. In some implementations, the titanium fluoride to reducing sub-cycle ratio is about 1 or less, and TiF ₃ films having a nitrogen content of less than about 10 at.% can be produced. As the titanium fluoride to reducing sub-cycle ratio increases, the amount of fluoride in the film generally increases and the relative TiF ₃ content increases, and the nitrogen content may also decrease. Without wishing to be bound by any theory, it is believed that, in some circumstances, a solid solution may form.

Deposition method

In some implementations, the thin film as described herein may be deposited by an atomic layer deposition (ALD) type method, a chemical vapor deposition (CVD) type method, or a combination method of ALD and CVD. In some implementations, other methods may be used, such as physical vapor deposition (PVD), plasma enhanced atomic layer deposition (PEALD), and the like.

Briefly, ALD-type methods are based on controlled self-limiting surface reactions of precursor chemicals. Gas phase reactions are prevented by providing the precursors alternately and sequentially into the reaction chamber. Gas phase reactants are separated from each other in the reaction chamber, for example by removing excess reactant and/or reaction byproducts from the reaction chamber between reaction pulses.

Briefly, a substrate is loaded into a reaction chamber and heated to an appropriate deposition temperature, usually at a reduced pressure. In some implementations, the substrate comprises a 300 mm silicon wafer. In some implementations, the substrate comprises a 450 mm silicon wafer. The deposition temperature is lower than the thermal decomposition temperature of the precursor, but is maintained at a level high enough to prevent condensation of the reactants and provide activation energy for the desired surface reaction. Of course, the appropriate temperature range for any given ALD reaction will depend on the surface end and reactive species involved.

A first reactant is guided or pulsed into the chamber in the form of a vapor phase pulse to contact the substrate surface. The conditions are preferably selected such that only one monolayer of precursor is adsorbed onto the substrate surface in a self-limiting manner. If there is an excess of first reactant and reaction byproducts, they are often purged from the reaction chamber with a pulse of an inert gas such as nitrogen or argon.

Purging the reaction chamber means removing gaseous precursors and/or gaseous by-products from the reaction chamber, for example, by evacuating the chamber with a vacuum pump and/or replacing the gas inside the reactor with an inert gas such as argon or nitrogen. Typical purge times are from about 0.05 to 20 seconds, more preferably from about 1 to 10, and even more preferably from about 1 to 2 seconds. However, other purge times may be used if desired, for example when it is necessary to deposit a layer over other structures with very high aspect ratio structures or complex surface morphologies. An appropriate pulsed time can be readily determined by one of ordinary skill in the art based on the particular circumstances.

A second gaseous reactant is pulsed into the chamber to react with the first reactant confined to the surface. Excess second reactant and gaseous by-products on the substrate surface are purged from the reaction chamber, preferably with the aid of an inert gas. The pulsing and purging steps are repeated until a thin film of the desired thickness is formed on the substrate, each cycle barely leaving a molecular monolayer. In forming the thin film disclosed herein, such as a film comprising TiF ₃ contained in TiN, for example, for depositing a dielectric transition metal compound material in the form of particles, and for depositing a conductive or semiconducting transition metal compound material. In each ALD super-cycle, two or more super-cycles are repeated one or more times.

Additional reactants to aid in the deposition process may also be supplied. These reactants may be provided in their own pulses or in conjunction with the precursor pulses and may be used, for example, to provide a desired surface terminus, or to strip or remove attached ligands and/or free by-products. In some embodiments, no additional reactants provide any species to the growing membrane.

If the precursors used in these methods are in the gaseous phase prior to being delivered to the reaction chamber and contacting the substrate surface, these precursors may be solid, liquid or gaseous materials under standard conditions (room temperature and atmospheric pressure).

As mentioned above, each pulse or phase of each cycle or super-cycle is preferably self-limiting. An excess of reactant precursor may be provided in each step to saturate the sensitive structural surface. Surface saturation provides good step coverage as it ensures reactant occupancy of all available reaction sites (eg, physical size or application of "sterically hindered" reactants). In some devices, the self-limiting behavior can be controlled, for example, by allowing some superposition of reactant pulses to balance the deposition rate against conformality (allowing some CVD-type reactions). In some implementations, the deposition methods described herein may partially include a CVD-type method or fully include a CVD-type method. Ideal ALD conditions with well-separated temporally and spatially separated reactants provide near-perfect self-limiting behavior and thus maximum conformality, but steric hindrance results in less than one molecular layer per cycle. A limited CVD reaction combined with a self-limiting ALD reaction can speed up the deposition.

"Pulsing" the vaporized reactant onto the substrate means that the vapor is delivered into the chamber for a limited time. Typically, the pulsed time is about 0.05 to 10 seconds. However, depending on the substrate type and its surface area, the pulsing time can be much longer than about 10 seconds.

As an example, for a 300 mm wafer in a single wafer ALD reactor, the precursors are generally from about 0.05 seconds to about 10 seconds, more preferably from about 0.1 seconds to about 5 seconds, and most preferably from 0.3 seconds to about 3.0 seconds. pulsed However, the pulsed time may optionally be in minutes. The optimal pulsing time can be readily determined by one of ordinary skill in the art based on the particular circumstances.

The mass flow rate of the metal precursor can be determined by one of ordinary skill in the art. In some embodiments, for example, for deposition on 300 mm wafers, the flow rate of the reactants is preferably without limitation from about 1 sccm to about 1000 sccm, from about 10 sccm to about 800 sccm, or from about 50 sccm to about 500 sccm.

The pulsing time and mass flow rate of each of the reactants can be independently selected. In some implementations, the pulsed time (and/or mass flow rate) of the two or more reactants is the same, whereas in some implementations the pulsed time (or mass flow rate) is different.

The pressure in the reaction chamber is typically from about 0.01 mbar to about 20 mbar, more preferably from about 1 mbar to about 10 mbar. However, in some cases, the pressure will be higher or lower than this range, as can be readily determined by one of ordinary skill in the art depending on a number of variables such as the particular reactor use, process and precursors.

Prior to initiating deposition of the film, the substrate may be heated to an appropriate growth temperature, as discussed above. The preferred deposition temperature may vary depending on a number of factors, including, without limitation, the composition of the substrate, including, without limitation, the reactant precursors, pressure, flow rate, arrangement of the reactor, and the nature of the material to be deposited thereon. For special circumstances, a particular growth temperature can be selected by one skilled in the art.

In some embodiments, the deposition temperature is from about 100°C to about 700°C, from about 200°C to about 500°C, from about 250°C to about 400°C, or from about 325°C to about 375°C.

The process time depends in part on the thickness of the layer to be produced, the composition of the film, the growth rate of the individual deposition sub-cycles and the total growth rate.

Examples of suitable reactors that can be used include commercially available ALD equipment such as the F-120 ^® reactor, Pulsar ^® reactor and Advance ^® 400 series available from ASM America of Phoenix, Arizona and ASM Europe BV of Almer, The Netherlands, The Netherlands. including a reactor. In addition to these ALD reactors, many other types of reactors capable of ALD growth of thin films may be used, including properly equipped CVD reactors and means for pulsing precursors. In some embodiments, a fluidized ALD reactor is used.

In some embodiments, the reactor is a batch reactor capable of receiving more than about 50 substrates, more than about 100 substrates, or more than about 125 substrates. In some embodiments, the reactor is a small-batch reactor and has 2 to about 20 substrates, 3 to about 15 substrates, or 4 to about 10 substrates. In some implementations, the substrate is a silicon wafer, such as a silicon wafer having a diameter of at least about 150 mm. In some implementations, the substrate is a silicon wafer having a diameter of at least about 200 mm or about 300 mm. In some implementations, the substrate can be a silicon wafer having a diameter of at least about 450 mm.

The ALD method for depositing conductive films comprising metal fluoride described herein may optionally be performed in a reactor or reaction space coupled to a cluster tool. In a cluster tool, since each reaction space is dedicated to one type of process, the temperature of the reaction space within each module can be kept constant, which is a throughput compared to reactors where the substrates are heated to the process temperature before each run. to improve

The stand-alone reactor may be equipped with a load-lock. In this case, there is no need to cool the reaction space between each run.

In some implementations, a CVD method is used in which two or more precursor materials are simultaneously contacted with a substrate in a reaction chamber. In some embodiments, for example, a metal fluoride precursor, a reducing agent, and a nitrogen reactant are simultaneously provided to a reaction chamber to react on a heated substrate surface to form a thin film comprising a conductive or semiconducting transition metal compound phase and a dielectric transition metal compound phase to form In some embodiments, the composition and structure of the deposited thin film can be controlled by the relative rates at which the metal fluoride precursor, reducing agent, and nitrogen reactant flow into the reaction space.

In some implementations, a CVD method is used, wherein two or more precursor materials having different compositions are simultaneously applied to a substrate in a reaction chamber. In some implementations, a CVD method is used, wherein two or more precursor materials having different concentrations are simultaneously applied, at least in part, to a substrate in a reaction chamber. In some implementations, the metal fluoride precursor, reducing agent, and nitrogen reactant are separately pulsed into the reaction chamber in such a way that a metal fluoride precursor pulse partially overlaps with a subsequent reducing agent, and/or nitrogen reactant precursor pulse or pulses. get angry The reactants react on the heated substrate surface to form a thin film comprising a conductive or semiconducting transition metal compound phase and a dielectric transition metal compound phase. In some implementations, the metal fluoride precursor, reducing agent, and nitrogen reactant are pulsed into the reaction chamber in such a way that a reducing agent, and/or nitrogen reactant precursor pulse or pulses partially overlap a subsequent metal fluoride precursor pulse. . The reactants react on the heated substrate surface in the reaction chamber to form a thin film comprising a conductive or semiconducting transition metal compound phase and a dielectric transition metal compound phase.

In some implementations, a CVD method is used, wherein two or more precursor materials with low concentrations are simultaneously applied to a substrate in a reaction chamber. In some embodiments, metal fluoride precursor, reducing agent, and nitrogen reactant in very low concentrations (eg, to avoid gas phase reaction and to enable surface controlled reaction) are simultaneously provided to the reaction chamber to a heated substrate surface The phase reacts to form a thin film comprising a conductive or semiconducting transition metal compound phase and a dielectric transition metal compound phase.

In some embodiments, the CVD method is performed at a substrate temperature between about 100°C and about 800°C, preferably between 200°C and 600°C. The contact time, removal time and precursor concentration applied to embodiments using a CVD process comprising deposition cycles may be selected based on what is disclosed for the ALD method deposition cycles described herein. For example, a high or substantially higher concentration of the precursor may be, for example, a concentration applied to cycles of an ALD method, or a low or substantially lower concentration may be, for example, one-fifth of the precursor concentration in an ALD method; or preferably less than 1/10. In some embodiments where the precursor may be in partial simultaneous contact with the substrate, the first precursor contacting step may overlap the subsequent precursor contacting step by no more than 50%, preferably no more than 30%.

Deposition of thin films comprising a dielectric transition metal material in a conductive or semiconducting transition metal compound material.

As mentioned above and discussed in detail below, a conductive or semiconducting transition metal compound phase Films comprising a dielectric transition metal compound phase included in ? may be deposited using a dielectric transition metal compound deposition sub-cycle and a reductive sub-cycle. In some embodiments, the transition metal can be selected from Ti, Ta, Nb, Mo, and W. The two sub-cycles can be repeated at the desired rate in the super-cycle to form a smooth/smooth nanocrystalline film. In some embodiments, thin films, such as thin films comprising a dielectric transition metal compound phase, do not have a columnar grain structure. In some embodiments, the thin films include a dielectric transition metal compound phase incorporated on a conductive or semiconducting transition metal compound.

In some implementations, the deposition method is an ALD method. In some implementations, the deposition process is a sequential or periodic method, such as a sequential or pulsed CVD method using the same precursor and condition selection as an ALD method. In some implementations, the deposition method is a PECVD method. In some implementations, the deposition method is an LPCVD/RTCDV method. In some implementations, the deposition method has steps that are not self-limiting. In some implementations, the method may operate in process conditions close to CVD conditions, or optionally fully CVD conditions.

In some embodiments, a thin film comprising a dielectric transition metal compound phase is deposited by a method that can include multiple super-cycles, wherein each super-cycle comprises at least one DM (dielectric transition metal compound) sub-cycle. -cycle and at least one reducing sub-cycle. The ratio of DM sub-cycles and reductive sub-cycles in each super-cycle can be varied to achieve a desired composition, and the number of super-cycles can be selected to deposit a film comprising a dielectric transition metal compound phase of a desired thickness. have. In some embodiments, the number of each sub-cycle performed successively in a super-cycle is limited to form a homogeneous conductive thin film, such as a film comprising a metal fluoride, where DM and CM (conductivity) are formed. or semiconducting transition metal compounds) are not visible in, for example, TEM or SEM cross-sectional images. In some embodiments, the number of successive sub-cycles performed in a super-cycle is limited such that a film comprising a dielectric transition metal compound phase (DM) comprised in a conductive or semiconducting transition metal compound phase (CM) is formed. where distinct DM particles can be seen, for example, in TEM or SEM cross-sectional images.

A super-cycle can be described as:

a [ b (DM) + c (reductant + nitrogen compound), where DM represents the dielectric transition metal sub-cycle, and b is the number of DM sub-cycles in each super-cycle; (reducing agent+nitrogen compound) denotes a reducing sub-cycle, c is the number of reducing sub-cycles in each super-cycle, and a is the number of super-cycles. The ratio of dielectric transition metal compound to reducing sub-cycles can be given as b:c .

The first and second deposition sub-cycles b and c may be provided at selected rates to deposit films having a desired composition and desired properties. For example, in some embodiments, the ratio ( b:c ) of the first dielectric transition metal compound deposition sub-cycle to the second reducing sub-cycle in one or more super-cycles is from about 0.01 to about 100, from about 0.05 to from about 50, or from about 0.1 to about 1. In some embodiments, the ratio of the dielectric transition metal compound adsorption sub-cycle to the reducing sub-cycle in one or more super-cycles is less than one. In some embodiments, the ratio of the dielectric transition metal compound adsorption sub-cycle to the reducing sub-cycle in the one or more super-cycles is from about 1 to about 3. In some embodiments, the ratio of the dielectric transition metal compound adsorption sub-cycle to the reducing sub-cycle in one or more super-cycles is from about 1 to about 50, from about 3 to about 30, or from about 5 to about 20. In some embodiments, the ratio of dielectric transition metal compound adsorption sub-cycle to reducing sub-cycle in one or more super-cycles is about 0.5, about 1, about 3, about 5, about 10, about 20, about 40, or about 50.

In some embodiments, the ratio of the first dielectric transition metal compound adsorption sub-cycle to the second reducing sub-cycle ( b:c ) is the same in all of the complete super-cycles performed in this method. In other embodiments, the specific ratio of the first dielectric transition metal compound adsorption sub-cycle to the second reducing sub-cycle can be varied in different complete sub-cycles. One skilled in the art can select specific ratios to provide the desired amount of the dielectric transition metal compound phase and the conductive or semiconducting transition metal compound phase in the film to obtain a film having the desired properties.

Although referred to as a first dielectric transition metal compound adsorption sub-cycle and a second reducing sub-cycle, in some embodiments, one or more super-cycles begin with a reducing sub-cycle, (after repeating the desired number of times) then A dielectric transition metal compound adsorption sub-cycle (the desired number of times may be repeated before starting another super-cycle) is performed.

In some embodiments, a super-cycle can be described as:

a [ b (DM+reductant)+ c (nitrogen reactant)], b is the number of DM sub-cycles (including reducing agent) in each super-cycle; c is the number of nitrogen reactant sub-cycles in each super-cycle, and a is the number of super-cycles. The ratio of dielectric transition metal compound to nitrogen sub-cycles can be given as b:c .

In some embodiments, the metal or M comprises Ti, Ta, Nb, Mo, or W.

In some embodiments, the reducing agent comprises a silane or borane. In some embodiments, the reducing agent is silane, disilane or trisilane. In some embodiments, the reducing agent is borane, diborane or triborane. As noted above, although referred to as a “reducing agent,” in some embodiments, it is not necessary for the actual chemical reduction to occur. Similarly, in some embodiments, reduction does not necessarily occur in a “reducing sub-cycle”.

In some embodiments, the nitrogen precursor can be selected from the group consisting of ammonia, N ₂ H ₄ , a nitrogen atom, a nitrogen containing plasma or nitrogen radicals or other species generated in the plasma.

In some embodiments, a thermal ALD method is used to deposit the fluoride film, and the N-precursor is ammonia or N ₂ H ₄ . In some implementations, a plasma ALD method is used, wherein the N-precursor for depositing the conductive fluoride containing film comprises a nitrogen atom, a nitrogen containing plasma, or a nitrogen radical.

Although the process conditions described for these methods can be applied to the deposition of other films comprising a dielectric transition metal compound phase, for the deposition of an exemplary thin film comprising TiF ₃ , a thin film comprising TiF ₃ contained in TiN, Specific process conditions and parameters are provided.

In some implementations, the first and second deposition sub-cycles are performed at the same reaction temperature. In some embodiments, the deposition temperature for one or both of the dielectric transition metal compound and the reducing sub-cycle is from about 100 °C to about 700 °C, from about 200 °C to about 500 °C, from about 250 °C to about 400 °C, or from about 325°C to about 375°C. In some embodiments, both the TiF ₄ and the reducing sub-cycle are performed at about 350° C.

In some embodiments, the ratio of the dielectric transition metal compound sub-cycle to the reducing sub-cycle is closed with a very thin thickness, such as less than about 3 nm, where closed is, for example, as determined by LEIS. , meaning that atoms of the underlying substrate are no longer detected at the outermost surface) are selected to deposit the film. In some implementations, the ratio of sub-cycles is such that the film is electrically continuous, ie, at very thin thicknesses, such as less than about 3 nm, less than about 2 nm, less than about 1.5 nm, or even less than about 1.0 nm. selected to conduct current. In some embodiments, the ratio of sub-cycles is such that the film is continuous as a layer, but very thin in a continuous matrix, such as less than about 3 nm, less than about 2 nm, less than about 1.5 nm, even about 1, It is selected to include some discontinuous features, such as holes, at a thickness of less than 0 nm. In some implementations, the ratio of sub-cycles is very thin, such as less than about 3 nm, less than about 2 nm, less than about 1.5 nm, even less than about 1.0 nm, although the film may not be closed and continuous. is chosen to still act as a diffusion barrier at its thickness.

In some implementations, the ratio of dielectric transition metal compound sub-cycle to reductive sub-cycle is selected to deposit a film that is photoactive, such as a film capable of absorbing the radiant energy of one or more photons to produce electrical energy in an electrical circuit. do. In some implementations, the ratio of dielectric transition metal compound sub-cycle to reductive sub-cycle is selected to deposit a thin film that will absorb at least a portion of the light incident on the thin film to create a potential difference within the thin film. In some implementations, the ratio of the dielectric transition metal compound sub-cycle to the reducing sub-cycle is selected to deposit a thin film that is electrically conductive and transmits light, eg, at least a portion of the light incident on the surface of the thin film passes through the thin film. do. In some implementations, the ratio of the dielectric transition metal compound sub-cycle to the reductive sub-cycle can transmit information contained in a modulated light beam incident on the surface of a thin film, such as a thin film, that can act as a waveguide as electromagnetic waves within the thin film. selected to deposit a film.

In some embodiments, increasing the relative number of reducing sub-cycles in each super-cycle increases the sheet resistance and/or resistivity of a film comprising a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase.

In some embodiments, a film comprising a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase formed according to the present disclosure is less than about 200,000 Ω/sq, less than about 140,000 Ω/sq, less than about 20,000 Ω/sq, It may have a sheet resistance of less than about 10,000 Ω/sq, less than about 1,000 Ω/sq, or even less than about 1,000 Ω/sq.

In some embodiments, a film comprising a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase formed in accordance with the present disclosure can have a layer resistivity of less than about 10 ⁷ μΩcm. In some embodiments, the thin film has a layer resistivity of about 500 μΩcm to about 5Х10 ⁶ μΩcm. In some embodiments, the thin film has a layer resistivity of about 5Х10 ³ μΩcm to about 5Х10 ⁶ μΩcm. In some embodiments, the thin film has a layer resistivity of about 10 ⁴ μΩcm to about 10 ⁶ μΩcm. In some embodiments, the thin film is not oxidized by ambient air below about 300°C.

In some embodiments, a film comprising a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase formed according to the present disclosure is at least about 500 μΩcm, at least about 1,000 μΩcm, at least about 5,000 μΩcm, or even at least about 10,000 μΩcm It can have a layer resistivity of In some embodiments, a film formed in accordance with the present disclosure includes particles on a dielectric transition metal compound incorporated on a conductive or semiconducting transition metal compound. In some embodiments, the dielectric transition metal compound phase particles have distinct grain boundaries with the conductive or semiconducting transition metal compound phase. In some embodiments, the dielectric transition metal compound phase particles include discrete particles surrounded by the conductive or semiconducting transition metal compound phase. In some embodiments, the particles of the discrete transition metal compound phase may be less than about 500 nm in diameter, preferably less than about 100 nm in diameter, and more preferably less than about 20 nm in diameter. In some embodiments, the particles on the dielectric transition metal compound may have a diameter of less than about 10 nm. In some embodiments, the average distance between the particles on the dielectric transition metal compound is less than about 50 nm, preferably less than about 20 nm. In some embodiments, the average distance between the particles on the dielectric transition metal compound is about 10 nm to about 20 nm. In some embodiments, the dielectric transition metal compound phase particles include columnar grains. In some embodiments, the columnar grains extend substantially throughout the thickness of the deposited thin film.

In some embodiments, a thin film comprising a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase is deposited on a substrate comprising silicon. In some implementations, the film is deposited on a substrate comprising at least one of Si, SiGe Ge, CdTe, GaAs, GaSb, InGaAs, or some other semiconductor material.

In some embodiments, a film formed according to the present disclosure comprising a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase is less than about 500° C., less than about 400° C., less than about 300° C. in an atmosphere containing oxygen. , or substantially no oxidation at temperatures below about 250°C. In some embodiments, the films are resistant to oxidation even for extended periods of time at room temperature or at naturally occurring temperatures, such as from about -50°C to about 50°C, in an oxygen-containing atmosphere, such as ambient air. For example, according to some embodiments, films formed according to the present methods may be resistant to oxidation even for more than 6 hours, preferably more than 24 hours, and in some cases, depending on the film composition, the film They may be resistant to oxidation for periods of more than 10 days, preferably more than 30 days, and in some cases, if desired, more than a year. In some embodiments, films formed in accordance with the present disclosure can be resistant to oxidation even for more than 10 years, or more than 20 years in the atmosphere. For example, exposure to ambient air is used as a protective layer against an atmosphere in which a film comprising metal fluoride may also contain moisture/water in some special applications, such as. Other atmospheres containing oxygen may contain oxygen atoms, plasma or radicals, ozone, water/moisture, or other species containing OH-groups.

metal fluoride Deposition of a thin film containing

As noted above and discussed in detail below, on films comprising a metal fluoride, such as a conductive or semiconducting transition metal compound. Films containing a metal fluoride phase included in the ? can be deposited using a metal fluoride deposition sub-cycle and a reducing sub-cycle. In some implementations, the metal can be selected from Ti, Ta, Nb, Mo, and W. The two sub-cycles can be repeated at the desired rate in the super-cycle to form a smooth/smooth nanocrystalline film. In some embodiments, thin films, such as thin films comprising metal fluoride, do not have a columnar grain structure. In some embodiments, the thin films include a dielectric transition metal compound phase incorporated on a conductive or semiconducting transition metal compound.

In some implementations, the deposition method is an ALD method. In some implementations, the deposition process is a sequential or periodic method, such as a sequential or pulsed CVD method using the same precursor and condition selection as an ALD method. In some implementations, the deposition method is a PECVD method. In some implementations, the deposition method is an LPCVD/RTCDV method. In some implementations, the deposition method has steps that are not self-limiting. In some implementations, the method may operate in process conditions close to CVD conditions, or optionally fully CVD conditions.

In some implementations, a thin film comprising metal fluoride is deposited by a method that can include multiple super-cycles, wherein each super-cycle includes at least one MF (Metal Fluoride) sub-cycle and at least one a reducing sub-cycle of The ratio of the MF sub-cycles to the reducing sub-cycles in each super-cycle can be varied to achieve a desired composition, and the number of super-cycles can be selected to deposit a fluoride containing film of a desired thickness. In some embodiments, the number of each sub-cycle successively performed in a super-cycle is limited to form a homogeneous conductive thin film, eg, a homogeneous conductive thin film, such as a film comprising a metal fluoride, where MF and MN are No distinct layers are visible, for example, in TEM or SEM cross-sectional images. In some embodiments, the number of consecutive sub-cycles performed in a super-cycle is limited such that a film comprising a dielectric transition metal fluoride phase (MF) included in a conductive or semiconducting transition metal compound phase (MN) is formed. where distinct MF particles can be seen, for example, in TEM or SEM cross-sectional images.

A super-cycle can be described as:

a [ b (MF) + c (reducing agent+nitrogen compound), where MF represents M _x F _y sub-cycles, b is the number of DM sub-cycles in each super-cycle; c is the number of reducing sub-cycles in each super-cycle; a is the number of super-cycles. The ratio of metal fluoride to reducing sub-cycle can be given as b:c .

The first and second deposition sub-cycles b and c may be provided at selected rates to deposit films having a desired composition and desired properties. For example, in some implementations, the ratio of the first metal fluoride deposition sub-cycle to the second reducing sub-cycle ( b:c ) in one or more super-cycles is from about 0.01 to about 100, from about 0.05 to about 50 , or from about 0.1 to about 1. In some embodiments, the ratio of the metal fluoride adsorption sub-cycle to the reducing sub-cycle in one or more super-cycles is less than one. In some embodiments, the ratio of the metal fluoride adsorption sub-cycle to the reducing sub-cycle in the one or more super-cycles is from about 1 to about 3. In some embodiments, the ratio of the metal fluoride adsorption sub-cycle to the reducing sub-cycle in one or more super-cycles is from about 1 to about 50, from about 3 to about 30, or from about 5 to about 20. In some embodiments, the ratio of metal fluoride adsorption sub-cycle to reducing sub-cycle in one or more super-cycles is about 0.5, about 1, about 3, about 5, about 10, about 20, about 40, or about 50 .

In some embodiments, the ratio of the first metal fluoride adsorption sub-cycle to the second reducing sub-cycle ( b:c ) is the same in all of the complete super-cycles performed in this method. In other implementations, the specific ratio of the first metal fluoride adsorption sub-cycle to the second reducing sub-cycle can be varied in different complete sub-cycles. A person skilled in the art can select a particular ratio to provide the desired amounts of metal, fluoride, and nitrogen in the film to obtain a film having the desired properties.

Although referred to as a first metal fluoride adsorption sub-cycle and a second reducing sub-cycle, in some embodiments, one or more super-cycles begin with a reducing sub-cycle, followed by (after repeating the desired number of times) the metal fluoride An adsorption sub-cycle (the desired number of times may be repeated before starting another super-cycle) is performed.

In some embodiments, a super-cycle can be described as:

a [ b (MF+reductant)+ c (nitrogen reactant)], b is the number of MF sub-cycles (including reducing agent) in each super-cycle; c is the number of nitrogen reactant sub-cycles in each super-cycle, and a is the number of super-cycles. The ratio of metal fluoride to nitrogen sub-cycle can be given as b:c .

In some embodiments, the metal or M comprises Ti, Ta, Nb, Mo, or W.

In some embodiments, the reducing agent comprises a silane or borane. In some embodiments, the reducing agent is silane, disilane or trisilane. In some embodiments, the reducing agent is borane, diborane or triborane. As noted above, although referred to as a “reducing agent,” in some embodiments, it is not necessary for the actual chemical reduction to occur. Similarly, in some embodiments, reduction does not necessarily occur in a “reducing sub-cycle”.

In some embodiments, the nitrogen precursor can be selected from the group consisting of ammonia, N ₂ H ₄ , a nitrogen atom, a nitrogen containing plasma or nitrogen radicals or other species generated in the plasma.

In some embodiments, a thermal ALD method is used to deposit the fluoride film, and the N-precursor is ammonia or N ₂ H ₄ . In some implementations, a plasma ALD method is used, wherein the N-precursor for depositing the conductive fluoride containing film comprises a nitrogen atom, a nitrogen containing plasma, or a nitrogen radical.

Although the process conditions described for these methods can be applied to the deposition of other films comprising fluoride, specific process conditions for the deposition of an exemplary thin film comprising TiF ₃ , a thin film comprising TiF ₃ contained in TiN. and parameters are provided.

In some implementations, the first and second deposition sub-cycles are performed at the same reaction temperature. In some embodiments, the deposition temperature for one or both of the metal fluoride and reductive sub-cycles is from about 100°C to about 700°C, from about 200°C to about 500°C, from about 250°C to about 400°C, or about 325°C. °C to about 375 °C. In some embodiments, both the TiF ₄ and the reducing sub-cycle are performed at about 350° C.

In some implementations, the ratio of the metal fluoride sub-cycle to the reducing sub-cycle is closed with a very thin thickness, such as less than about 3 nm, where closed is, for example, as determined by LEIS, lower (meaning that the atoms of the substrate are no longer detected at the outermost surface) are selected for depositing the film. In some implementations, the ratio of sub-cycles is such that the film is electrically continuous, ie, at very thin thicknesses, such as less than about 3 nm, less than about 2 nm, less than about 1.5 nm, or even less than about 1.0 nm. selected to conduct current. In some embodiments, the ratio of sub-cycles is such that the film is continuous as a layer, but very thin in a continuous matrix, such as less than about 3 nm, less than about 2 nm, less than about 1.5 nm, even about 1, It is selected to include some discontinuous features, such as holes, at a thickness of less than 0 nm. In some implementations, the ratio of sub-cycles is very thin, such as less than about 3 nm, less than about 2 nm, less than about 1.5 nm, even less than about 1.0 nm, although the film may not be closed and continuous. is chosen to still act as a diffusion barrier at its thickness.

In some implementations, the ratio of metal fluoride sub-cycle to reductive sub-cycle is selected to deposit a film that is photoactive, such as a film capable of absorbing the radiant energy of one or more photons to produce electrical energy in an electrical circuit. In some implementations, the ratio of metal fluoride sub-cycle to reductive sub-cycle is selected to deposit a thin film that will absorb at least a portion of light incident on the thin film to create a potential difference within the thin film. In some implementations, the ratio of metal fluoride sub-cycle to reductive sub-cycle is selected to deposit a thin film that is electrically conductive and transmits light, eg, at least a portion of the light incident on the surface of the thin film passes through the thin film. In some implementations, the ratio of the metal fluoride sub-cycle to the reductive sub-cycle is a thin film capable of acting as a waveguide, such as a film capable of transmitting information contained in a modulated light beam incident on the surface of the thin film as an electromagnetic wave within the thin film. selected to deposit.

In some embodiments, increasing the number of reducing sub-cycles in each super-cycle increases the sheet resistance and/or resistivity of the metal fluoride film.

In some embodiments, a fluoride-containing film formed according to the present disclosure is less than about 200,000 Ω/sq, less than about 140,000 Ω/sq, less than about 20,000 Ω/sq, less than about 10,000 Ω/sq, less than about 1,000 Ω/sq, or It can even have a sheet resistance of less than about 1,000 Ω/sq.

In some implementations, a fluoride-containing film formed in accordance with the present disclosure can have a layer resistivity of less than about 10 ⁷ μΩc. In some embodiments, the thin film has a layer resistivity of about 500 μΩcm to about 5Х10 ⁶ μΩcm. In some embodiments, the thin film has a layer resistivity of about 5Х10 ³ μΩcm to about 5Х10 ⁶ μΩcm. In some embodiments, the thin film has a layer resistivity of about 10 ⁴ μΩcm to about 10 ⁶ μΩcm. In some embodiments, the thin film is not oxidized by ambient air below about 300°C.

In some embodiments, a fluoride containing membrane according to the present disclosure is at least about 500 μΩcm, at least about 1,000 μΩcm, at least about 5,000 μΩcm, or even at least about 10,000 μΩcm It can have a layer resistivity of In some embodiments, a fluoride-containing film formed according to the present disclosure may include metal fluoride particles incorporated on a conductive or semiconducting transition metal compound. In some embodiments, the metal fluoride particles have distinct grain boundaries with the conductive or semiconducting transition metal compound phase. In some embodiments, the metal fluoride particles include discrete particles surrounded by the conductive or semiconducting transition metal compound phase. In some embodiments, the metal fluoride particles may have a diameter of less than about 500 nm, preferably less than about 100 nm in diameter, and more preferably less than about 20 nm in diameter. In some embodiments, the metal fluoride particles may have a diameter of less than 10 nm. In some embodiments, the average distance between the metal fluoride particles is less than about 50 nm, preferably less than about 20 nm. In some embodiments, the average distance between the metal fluoride particles is about 10 nm to about 20 nm. In some embodiments, the metal fluoride particles include columnar grains. In some embodiments, the columnar grains extend substantially throughout the thickness of the deposited thin film.

In some implementations, the fluoride containing film is deposited on a substrate comprising silicon. In some implementations, the fluoride containing film is deposited on a substrate comprising at least one of Si, SiGe Ge, CdTe, GaAs, GaSb, InGaAs, or some other semiconductor material.

In some embodiments, a film comprising a metal fluoride, formed according to the present disclosure, is substantially oxidized at a temperature of less than about 500 °C, less than about 400 °C, less than about 300 °C, or less than about 250 °C in an atmosphere containing oxygen. does not indicate In some embodiments, the films are resistant to oxidation even for extended periods of time at room temperature or at naturally occurring temperatures, such as from about -50°C to about 50°C, in an oxygen-containing atmosphere, such as ambient air. For example, according to some embodiments, films formed according to the present methods may be resistant to oxidation even for more than 6 hours, preferably more than 24 hours, and in some cases, depending on the film composition, the film They may be resistant to oxidation for periods of more than 10 days, preferably more than 30 days, and in some cases, if desired, more than a year. In some embodiments, films formed in accordance with the present disclosure can be resistant to oxidation even for more than 10 years, or more than 20 years in the atmosphere. For example, exposure to ambient air is used as a protective layer against an atmosphere in which a film comprising metal fluoride may also contain moisture/water in some special applications, such as. Other atmospheres containing oxygen may contain oxygen atoms, plasma or radicals, ozone, water/moisture, or other species containing OH-groups.

of a thin film comprising a dielectric transition metal material in a conductive or semiconducting transition metal compound material. ALD deposition

As noted above, in some embodiments, an atomic layer deposition method for depositing films comprising a dielectric transition metal compound phase, such as a thin film comprising a fluoride compound incorporated on a conductive or semiconducting transition metal compound, includes multiple , wherein each super-cycle comprises at least one dielectric transition metal compound phase (DM) sub-cycle and at least one reducing sub-cycle. In the DM sub-cycle, the substrate is exposed to a gaseous dielectric transition metal compound, such as a metal fluoride, to adsorb to the extent of a monolayer on the substrate surface. In the reducing sub-cycle, the substrate is exposed to a reducing agent such as silane or borane and a nitrogen reactant. The ratio of DM sub-cycles and reductive sub-cycles can be varied to achieve a desired composition, and the number of super-cycles can be selected to deposit a film comprising a dielectric transition metal compound phase of a desired thickness. The DM sub-cycle may precede the reducing sub-cycle and vice versa. Similarly, in a reducing cycle, the reducing agent may be provided prior to the nitrogen reactant and vice versa.

1 depicts an ALD method for forming a film on a substrate comprising a dielectric transition metal compound phase and a conductive or semiconducting transition metal compound phase in a reaction chamber comprising multiple ALD super-cycles 100 . Each super-cycle includes a first DM deposition sub-cycle 200 and a second reducing sub-cycle 300 . The super-cycle 100 is repeated a desired number of times to deposit a thin film of a desired thickness. The ratio between sub-cycles 200 and 300 in super-cycle 100 can be selected to obtain a film having a desired composition and properties.

The first dielectric transition metal compound deposition sub-cycle comprises:

vaporized dielectric transition metal compounds such as metal fluorides forming (210) a maximum monomolecular layer of the dielectric transition metal compound on a substrate by pulsing in a reaction chamber;

purging the reaction chamber to remove excess dielectric transition metal compounds and reaction by-products, if any (220); and

repeating the pulsing step and the purging step (250).

In some implementations, the first deposition sub-cycle is repeated 1, 2, 3, 4, 5, 10, 20, 50, 100 or more times in succession. In some implementations, the first deposition sub-cycle is repeated continuously within about 30 to 60 times, continuously up to about 30 to about 50 times, or continuously up to about 40 times.

The atomic layer deposition super-cycle 100 for forming a thin film also includes one or more second reducing sub-cycles 300 . In some implementations, the second reducing sub-cycle 300 comprises:

pulsing a vaporized reducing agent, such as disilane or trisilane, into the reaction chamber to reduce (310) at least a portion of the adsorbed dielectric transition metal compound;

purging the reaction chamber to remove excess reducing agent and reaction byproducts, if any (320);

selectively providing 330 a pulse of a nitrogen reactant, such as NH ₃ , into the reaction chamber;

optionally purging the reaction chamber to remove excess nitrogen reactants and any gaseous byproducts (340); and

repeating (350) at least the pulsing step (310) and the purging step (320).

In some embodiments, the second reducing sub-cycle 300 is repeated 1, 2, 3, 4, 5, 10, 20, 50, 100 or more times in succession. In some embodiments, the second reducing sub-cycle is repeated about 3 to 6 times, or about 5 times.

The first and second sub-cycles 200 , 300 are repeated a number of times in the complete ALD super-cycle 100 , the complete ALD super-cycle 100 having a desired thickness including a desired concentration of the dielectric transition metal compound phase. is repeated to form a thin film of

In some implementations, the number of times the first deposition sub-cycle 200 and the second reducing sub-cycle 300 are repeated is the same in each complete ALD super-cycle 100 . In other implementations, the number of first and second sub-cycles 100 , 200 varies in one or more complete ALD super-cycles 100 . The number of first and second sub-cycles 100 , 200 in each complete ALD super-cycle 100 and the number of first and second sub-cycles 100 , 200 and the total ALD super-cycle 100 . The total number can be adjusted to deposit thin films of desired thickness and composition.

Although shown beginning with a first deposition sub-cycle 200 , each complete ALD cycle may begin and end with either the first sub-cycle 100 or the second sub-cycle 200 . For example, each ALD super-cycle to form a thin film may begin with a first dielectric transition metal compound deposition sub-cycle or a reductive sub-cycle. In some embodiments, one or more super-cycles may begin with a reducing sub-cycle.

In some implementations, the thin film is deposited by ALD on the substrate surface to form a 500 nm or less conformal thin film. In some embodiments, the thickness of the thin film is less than 100 nm, less than about 50 nm, less than about 10 nm. Depending on the application, the thickness can be much thinner, such as from about 2 to about 50 Angstroms, preferably from about 3 to about 30 Angstroms, and in some cases from about 5 to about 20 Angstroms. In some embodiments, when a film comprising TiF ₃ is used as a photoelectrode, the thickness of the film may be about 30 nm. In some embodiments, the thin film can have a thickness greater than about 100 nm, greater than about 1 μm, or in some instances greater than about 1 mm.

Various changes, omissions, and additions may be made to the methods and structures described above without departing from the scope of the present invention. All such modifications and variations are intended to fall within the scope of the invention as defined by the appended claims.

PVD deposition of thin films containing dielectric transition metal materials in conductive or semiconducting transition metal compound materials.

In some embodiments, thin films as described herein comprising a dielectric transition metal compound material within a conductive or semiconducting transition metal compound material may be deposited by a physical vapor deposition (PVD) type method. In some embodiments, a thin film comprising a dielectric transition metal compound material and a conductive or semiconducting transition metal compound material may be deposited by a reactive sputtering deposition method. In some implementations, a reactive sputtering method can include using a target comprising a transition metal element. For example, the target may include a transition metal target such as a titanium target. In some implementations, the deposition method can include generating a plasma in an atmosphere comprising nitrogen, fluorine, and/or oxygen species.

In some embodiments, the dielectric transition metal compound may include a solid transition metal fluoride, a transition metal oxide, or a transition metal oxyfluoride, or a mixture of one or more thereof. In some embodiments, the dielectric transition metal compound material may include TiF ₃ .

In some embodiments, the conductive or semiconducting transition metal compound material may include a transition metal nitride. In some embodiments, the conductive or semiconducting transition metal compound material may include TiN.

In some embodiments, the thin film is deposited using a sputtering method, such as a reactive sputtering method. In some embodiments, the sputtering method may include generating a plasma in an atmosphere containing nitrogen and/or fluorine. In some embodiments, the atmosphere may include nitrogen-containing species and/or fluorine-containing species. In some embodiments, the atmosphere is, for example, N ₂ , NH ₃ , and/or F ₂ .

In some implementations, a thin film comprising TiF ₃ in TiN is deposited by a sputtering method, such as a reactive sputtering method. In some embodiments, the sputtering method may include generating a plasma in an atmosphere containing N ₂ and/or F ₂ . In some embodiments, the sputtering method may include generating a plasma in an atmosphere containing NH ₃ and/or F ₂ .

In some embodiments, the composition of the atmosphere may change during the deposition method. For example, the concentrations of the ?- and fluorine-containing species may vary throughout the deposition method. In some embodiments, the atmosphere may include nitrogen-containing species and may not include fluorine-containing species. In some embodiments, the atmosphere may include fluorine-containing species and may not include nitrogen-containing species. In some embodiments, during a deposition method, the atmosphere may include nitrogen-containing species and free of fluorine-containing species during at least a portion of the deposition method, such as during at least a different portion of the deposition method, such as a deposition method may contain fluorine-containing species and may not contain nitrogen-containing species during the initial or later part of

of a thin film comprising a dielectric transition metal material in a conductive or semiconducting transition metal compound material. ALD deposition

As noted above, in some embodiments, an atomic layer deposition method for depositing a thin film comprising a dielectric transition metal compound material within a conductive or semiconducting transition metal compound material may include multiple super-cycles, Each super-cycle comprises at least one transition metal compound sub-cycle and at least one second sub-cycle, such as a reducing sub-cycle. In the transition metal compound sub-cycle, the substrate is exposed to the vapor phase transition metal compound so as to be adsorbed to the extent of a monolayer on the substrate surface. In said second sub-cycle, such as a reducing sub-cycle, the substrate is exposed to other reactants, such as a reducing agent such as silane or borane and/or a third reactant such as a nitrogen reactant. The ratio of the transition metal compound sub-cycle to the second sub-cycle can be varied to achieve a desired composition, and the number of super-cycles can be selected to deposit a film comprising a transition metal compound phase of a desired thickness. The transition metal compound sub-cycle may proceed before the second sub-cycle, and vice versa. Similarly, in a second sub-cycle, such as a reducing sub-cycle, the reducing agent may be provided prior to a third reactant, such as a nitrogen reactant, and vice versa.

TIF ₃ cast membrane containing ALD deposition

As noted above, in some embodiments, atomic layer deposition to deposit a film comprising TiF ₃ in a conductive or semiconducting transition metal compound, such as TiN, such as a thin film comprising a TiF _x compound, such as TiF ₃ . The method may comprise multiple super-cycles, each super-cycle comprising at least one TiF ₄ sub-cycle and at least one reducing sub-cycle. In the TiF ₄ sub-cycle, the substrate is exposed to vapor phase TiF ₄ to be adsorbed to the extent of a monolayer on the substrate surface. In the reducing sub-cycle, the substrate is exposed to a reducing agent such as silane or borane and a nitrogen reactant. The ratio of TiF ₄ sub-cycles and reducing sub-cycles can be varied to achieve a desired composition, and the number of super-cycles can be selected to deposit a film comprising titanium fluoride of a desired thickness. The TiF ₄ sub-cycle may be performed prior to the reducing sub-cycle and vice versa. Similarly, in a reducing cycle, the reducing agent may be provided prior to the nitrogen reactant and vice versa.

In some embodiments, the TiF ₄ sub-cycle may include a reducing agent, such as a silane compound or a borane compound. And, in some embodiments, the second sub-cycle does not include a silane or borane compound.

A super-cycle can be described as:

a [ b (titanium fluoride) + c (reductant + nitrogen compound), where (titanium fluoride) represents TiF ₄ sub-cycle and b is the number of TiF ₄ sub-cycles in each super-cycle; (reducing agent+nitrogen compound) denotes a reducing sub-cycle, c is the number of reducing sub-cycles in each super-cycle; a is the number of super-cycles. Although the TiF ₄ sub-cycle is shown first in the super-cycle, in some implementations, in one or more super-cycles, the reducing sub-cycle comes first. Thus, in some embodiments, a TiF ₄ sub-cycle can be considered a first sub-cycle and a reducing sub-cycle can be considered a second sub-cycle, whereas in some embodiments, a reducing sub-cycle can be considered The cycle may be considered a first sub-cycle and the TiF ₄ sub-cycle may be considered a second sub-cycle.

In some embodiments, a super-cycle can be described as:

a [ b (TiF ₄ +reductant)+ c (nitrogen reactant)], b is the number of TiF ₄ sub-cycles (including reducing agent) in each super-cycle; c is the number of nitrogen reactant sub-cycles in each super-cycle, and a is the number of super-cycles. The ratio of metal fluoride to nitrogen sub-cycle can be given as b:c .

In some embodiments, the reducing agent may be a borane or a silane, such as diborane, triborane, disilane, or trisilane. In some embodiments, the reducing agent is disilane. In some embodiments, the reducing agent is trisilane. In some embodiments, the nitrogen reactant may be ammonia, N ₂ H ₄ , a nitrogen atom, a nitrogen containing plasma, or a nitrogen radical.

In some embodiments, a super-cycle can be described as a [ b (TiF ₄ ) + c (Si ₂ H ₆ +NH ₃ )], where b is the number of TiF ₄ sub-cycles in each super-cycle , c is the number of reducing sub-cycles in each super-cycle, and a is the number of super-cycles.

Thus, the ratio of TiF ₄ sub-cycle to reducing sub-cycle can be given as b:c (or TiF ₄ :reducing). In some implementations, the ratio of sub-cycles in each ALD super-cycle of the ALD method is constant. In other implementations, the ratio of sub-cycles in one or more super-cycles may vary. Unless otherwise indicated, when a ratio of sub-cycles is provided herein, the ratio refers to the ratio of sub-cycles in a complete ALD method comprising multiple super-cycles.

In some implementations, the first and second deposition sub-cycles are performed at the same reaction temperature. In some embodiments, the deposition temperature for one or both of TiF ₄ and the reducing sub-cycle is from about 100 °C to about 700 °C, from about 200 °C to about 500 °C, from about 250 °C to about 400 °C, or about 325 °C. °C to about 375 °C. In some embodiments, both the TiF ₄ and the reducing sub-cycle are performed at about 350° C.

In some embodiments, the first and second sub-cycles are performed in the same reactor.

The first and second sub-cycles may be provided in a ratio selected to deposit a film having a desired composition and desired properties. For example, in some implementations, the ratio of the first TiF ₄ deposition sub-cycle to the second reducing sub-cycle in one or more ALD super-cycles is about 0.01 to about 100, about 0.05 to about 50, or about 0.1 to about 1. In some implementations, the ratio of the TiF ₄ deposition sub-cycle to the reducing sub-cycle in one or more super-cycles is less than one. In some implementations, the ratio of the TiF ₄ deposition sub-cycle to the reducing sub-cycle in the one or more super-cycles is from about 1 to about 3. In some embodiments, the ratio of TiF ₄ deposition sub-cycle to reducing sub-cycle in one or more super-cycles is from about 1 to about 50, from about 3 to about 30, or from about 5 to about 20. In some embodiments, the ratio of TiF ₄ deposition sub-cycle to reducing sub-cycle in one or more super-cycles is about 0.01, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.8, or about 1. .

As noted above, the ratio of sub-cycles can be selected to achieve a desired composition and desired film properties. In some embodiments, by increasing the number of reducing sub-cycles compared to TiF ₄ sub-cycles, a greater proportion of TiF ₄ is converted to TiF ₃ . In some implementations, the ratio of TiF ₄ to reducing sub-cycle is increased to increase the sheet resistance and/or resistivity of the deposited film.

In some implementations, the ratio of the first TiF ₄ deposition sub-cycle to the second reducing sub-cycle is the same in all of the complete super-cycles performed in this ALD method. In other implementations, the specific ratio of the first TiF ₄ deposition sub-cycle to the second reducing sub-cycle can be varied in different full ALD sub-cycles. A person skilled in the art can select a particular ratio to provide the desired amounts of titanium, fluoride, and nitrogen in the film to obtain a film having the desired properties.

In some implementations, the deposited film comprising TiF ₃ is a conductive film. In some implementations, a film comprising TiF ₃ is deposited, which film does not contain fluorine in the film and has a higher oxidation level than a TiN film deposited by known vapor deposition methods, such as a TiN film deposited by ALD. Resistant (eg, when measured at 300° C. in ambient air).

In some embodiments, a conductive film comprising TiF ₃ is formed, the film comprising some silicon or boron from the reducing compound and some nitrogen from the nitrogen reactant. For example, in some embodiments, a conductive thin film comprising TiF ₃ is deposited, which thin film contains some Si and some N.

In some embodiments, silane is used as a reducing agent and the film comprising TiF ₃ also comprises a small amount of silicon. For example, in some embodiments, the silicon content is from about 15 at% to, preferably from about 0.01 to about 10 at%, more preferably from about 0.1 to about 5 at%, and most preferably from about 0.1 to about 10 at%. It may be in the range of about 2 at%. In some embodiments, the silicon content is preferably less than about 1.5 at%.

In some embodiments, borane is used as a reducing agent and the film comprising TiF ₃ also includes a small amount of boron. For example, in some embodiments, the boron content can range from less than about 15 at%, from about 0.01 to about 10 at%, from about 0.1 to about 5 at%, or from about 0.1 to about 2 at%. In some embodiments, the boron content is preferably less than about 1.5 at%.

In some implementations, films comprising TiF ₃ also include a small amount of nitrogen. For example, in some embodiments, the nitrogen content can range from about 0.5 to about 50 at%, from about 1 to 20 at%, or from about 2 to about 15 at%.

In some embodiments, the films include fluorine in an amount greater than about 10 at%, preferably from about 20 to about 75 at%, from about 40 to about 70 at%, or from about 45 to about 65 at%.

In some embodiments, films comprising TiF ₃ include less than about 1 at% oxygen.

In some embodiments, the deposited film comprising TiF ₃ comprises TiF ₃ particles incorporated on a conductive or semiconducting transition metal compound. In some embodiments, the TiF ₃ particles have distinct grain boundaries with the conductive or semiconducting transition metal compound phase. In some embodiments, the TiF ₃ particles include discrete particles surrounded by the conductive or semiconducting transition metal compound phase. In some embodiments, the TiF ₃ particles may have a diameter of less than about 500 nm, preferably less than about 100 nm in diameter, and more preferably less than about 20 nm in diameter. In some embodiments, the TiF ₃ particles may have a diameter of less than 10 nm. In some embodiments, the average distance between the TiF ₃ particles is less than about 50 nm, preferably less than about 20 nm. In some embodiments, the average distance between the TiF ₃ particles is about 10 nm to about 20 nm. In some embodiments, the TiF ₃ particles include columnar grains. In some embodiments, the columnar grains extend substantially throughout the thickness of the deposited thin film.

In some implementations, a film comprising TiF ₃ is deposited on a substrate comprising silicon. In some implementations, a film comprising TiF ₃ is deposited on a substrate comprising at least one of Si, SiGe Ge, CdTe, GaAs, GaSb, InGaAs, or some other semiconductor material.

FIG. 2 shows an ALD method for forming a film comprising TiF ₃ on a substrate in a deposition chamber comprising multiple ALD super-cycles 101 . Each super-cycle includes a first TiF ₄ deposition sub-cycle 201 and a second reducing sub-cycle 301 . The super-cycle 100 is repeated a desired number of times to deposit a TiF ₃ film of a desired thickness. The ratio between sub-cycles 201 and 301 in super-cycle 101 can be selected to obtain a film having a desired composition and properties.

The first titanium fluoride deposition sub-cycle comprises:

pulsing vaporized TiF _x , such as TiF ₄ , into the reaction chamber to form a maximum monolayer of titanium fluoride on the substrate ( 211 );

purging the reaction chamber to remove excess titanium fluoride and reaction by-products, if any (221); and

repeating the pulsing step and the purging step ( 251 ).

In some implementations, the first deposition sub-cycle is repeated 1, 2, 3, 4, 5, 10, 20, 50, 100 or more times in succession. In some implementations, the first deposition sub-cycle is repeated continuously within about 30 to 60 times, continuously up to about 30 to about 50 times, or continuously up to about 40 times.

The atomic layer deposition super-cycle 101 for forming the TiF ₃ /TiN film also includes one or more second reducing sub-cycles 301 . In some implementations, the second reducing sub-cycle 301 comprises:

pulsing a vaporized reducing agent, such as disilane or trisilane, into the reaction chamber to reduce at least a portion of TiF ₄ to TiF ₃ ( 311 );

purging the reaction chamber to remove excess reducing agent and reaction by-products, if any ( 321 );

providing a pulse of a nitrogen reactant, such as NH ₃ , into the reaction chamber, wherein the nitrogen reactant causes at least some nitrogen to contribute to the titanium fluoride film (331);

purging the reaction chamber to remove excess nitrogen reactants and any gaseous byproducts (341); and

repeating the pulsing step and the purging step (351).

In some embodiments, the second reducing sub-cycle 301 is repeated 1, 2, 3, 4, 5, 10, 20, 50, 100 or more times in succession. In some embodiments, the second reducing sub-cycle is repeated about 3 to 6 times, or about 5 times.

The first and second sub-cycles 201, 301 are repeated multiple times in the complete ALD super-cycle 101, wherein the complete ALD super-cycle 101 contains the desired concentrations of titanium, fluoride, and nitrogen. Repeat to form a thick TiF ₃ film.

In some implementations, the number of times the first deposition sub-cycle 201 and the second reducing sub-cycle 301 are repeated is the same in each complete ALD super-cycle 100 . In other implementations, the number of first and second sub-cycles 101 , 201 varies in one or more complete ALD super-cycles 101 . The number of first and second sub-cycles 101 , 201 in each complete ALD super-cycle 101 and the number of first and second sub-cycles 101 , 201 and the total ALD super-cycle 101 . The total number can be adjusted to deposit TiF ₃ /TiN films of desired thickness and composition.

Although shown beginning with a first deposition sub-cycle 201 , each complete ALD cycle may begin and end with either the first sub-cycle 101 or the second sub-cycle 201 . For example, each ALD super-cycle to form a thin film may begin with a first titanium fluoride deposition sub-cycle or a reductive sub-cycle. In some embodiments, one or more super-cycles may begin with a reducing sub-cycle.

In some implementations, a film comprising TiF ₃ is deposited on the substrate by ALD to form a conformal thin film of 500 nm or less. In some embodiments, the thickness of the thin film is less than 100 nm, less than about 50 nm, less than about 10 nm. Depending on the application, the thickness can be much thinner, such as from about 2 to about 50 Angstroms, preferably from about 3 to about 30 Angstroms, and in some cases from about 5 to about 20 Angstroms. In some embodiments, when a film comprising TiF ₃ is used as a photoelectrode, the thickness of the film may be about 30 nm. In some embodiments, the thin film can have a thickness greater than about 100 nm, greater than about 1 μm, or in some instances greater than about 1 mm.

In some embodiments, a film comprising TiF ₃ is formed by just starting to oxidize in an oxygen or water/moisture containing atmosphere, such as ambient air at a temperature greater than about 300°C.

Various changes, omissions, and additions may be made to the methods and structures described above without departing from the scope of the present invention. All such modifications and variations are intended to fall within the scope of the invention as defined by the appended claims.

optical element

The methods and materials described herein can provide films with photoactive or other desired properties for use in photovoltaic or optical devices, such as solar cells or waveguide devices. According to some embodiments, during optical device fabrication, composite thin films are deposited by the disclosed methods on a suitable substrate, such as a p-type silicon substrate.

In some embodiments, a thin film or optical device as described herein can operate or be activated at at least wavelengths of light corresponding to radiation from the sun. In some embodiments, the thin film or optical device operates or is activated at a light wavelength of at least about 100 nm to about 3000 nm. In some embodiments, the thin film or optical device operates or is activated at least at a wavelength of visible light. In some embodiments, the thin film or optical device operates or is activated at a wavelength of at least greater than about 350 nm or greater than about 500 nm. In some embodiments, the thin film or optical device operates or is activated at a wavelength corresponding to at least the red color of the visible light spectrum. In some embodiments, the thin film or photonic device operates or activates at least at a radiation wavelength at which a typical solar cell can operate, such as about 532 nm, and/or about 630 nm to about 680 nm, etc., as known to those skilled in the art. do.

In some embodiments, an optical device may include a first conductive or semiconducting transition metal layer, a second semiconducting layer positioned over the first layer, and a third composite film layer positioned over the second layer. In some embodiments, the layers are solid layers. In some embodiments, the layers do not include a liquid.

In some embodiments, the first conductive or semiconducting transition metal layer can act as an electrical contact for an optical device. In some embodiments, the first layer may include a conductive or semiconducting transition metal oxide or nitride. In some embodiments, the first layer may include a metal selected from Ti, Ta, Nb, Mo, and W. In some embodiments, the first layer may include TiN. In some embodiments, the first layer is a solid. In some embodiments, the first layer is not a liquid. In some embodiments, the thickness of the first layer is less than 500 nm. In some embodiments, the thickness of the first layer is less than 100 nm, preferably less than about 50 nm. In some embodiments, the thickness of the first layer is 45 nm.

In some implementations, the second layer may include at least one of Si, SiGe, Ge, CdTe, GaAs, GaSb, InGaAs or some other semiconducting material, such as III-V or II-VI materials. In some embodiments, the second layer may include p ⁺ -type silicon. In some embodiments, the second layer may further include an oxide layer. In some embodiments, the second layer may include an oxide layer, such as SiO ₂ , on the top surface, the bottom surface, or both the top and bottom surfaces. In some embodiments, the oxide layer or layers may include a native oxide or a thermal oxide. In some embodiments, the second layer is a solid. In some embodiments, the second layer is not a liquid. In some embodiments, the oxide layer or layers may be less than about 50 nm thick, preferably less than about 20 nm thick. In some embodiments, the oxide layer or layers can be less than about 10 nm thick, less than about 5 nm thick, or less than about 3 nm thick. In some embodiments, the second layer may be free of oxide on the top surface, the bottom surface, or both the top and bottom surfaces.

In some embodiments, the third layer may include a thin film as disclosed herein. In some embodiments, the third composite layer may include a dielectric transition metal compound phase included on a conductive or semiconducting transition metal compound. In some embodiments, the dielectric transition metal compound phase may include discrete particles. In some embodiments, the transition metal on the dielectric transition metal compound may be selected from one of Ti, Ta, Nb, Mo, and W. In some embodiments, the dielectric transition metal compound phase may be selected from a list comprising the following materials: TiF ₃ , Cr ₂ O ₃ , NiO, WO ₃ , Ti ₂ O ₃ , TiOF ₂ , NbO ₂ F, NbO _{3 - x} F _x , NbO _{x /2} F _3-x , MoO _{3 - x} F _x , MoO _x F _{3 -x} , TaO ₂ F, TaO _x F _{3 -x} , WO _3-x F _x . In some embodiments, the dielectric transition metal compound phase has a ReO ₃ structure. In some embodiments, the conductive or semiconducting transition metal compound phase can be selected from a list comprising Cr, TiN, Fe, W, TiC, Ti. In some embodiments, the dielectric transition metal compound phase includes TiF ₃ . In some embodiments, the conductive or semiconducting transition metal compound phase comprises TiN. In some embodiments, the dielectric transition metal compound phase includes TiF ₃ , and the conductive or semiconducting transition metal compound phase includes TiN. In some embodiments, the third layer includes a mixture of TiF ₃ and TiN.

In some embodiments, the dielectric transition metal compound phase may include particles of about 0.1 nm to about 500 nm. In some embodiments, the dielectric transition metal compound phase particles have distinct grain boundaries with the conductive or semiconducting transition metal compound phase. In some embodiments, the particles of the discrete transition metal compound phase may be less than about 500 nm in diameter, preferably less than about 100 nm in diameter, and more preferably less than about 20 nm in diameter. In some embodiments, the particles on the dielectric transition metal compound may have a diameter of less than about 10 nm. In some embodiments, the average distance between the particles on the dielectric transition metal compound is less than about 50 nm, preferably less than about 20 nm. In some embodiments, the average distance between the particles on the dielectric transition metal compound is about 10 nm to about 20 nm. In some embodiments, the dielectric transition metal compound phase particles include columnar grains. In some embodiments, the columnar grains extend substantially throughout the thickness of the third layer.

In some embodiments, the second layer can act as a photoactive component in an optical device. In some embodiments, the third layer can act as a photoactive component in an optical device. In some embodiments, the second and third layers can act as photoactive components in an optical device. In some implementations, the photoactive component absorbs the radiant energy of photons to generate electrical energy in a circuit, eg, the photoactive component can create a potential difference within the device upon exposure to incident light. In some embodiments, the photoactive component is configured to generate photons using electrical energy.

In some implementations, the third layer of the optical device includes a photon transmissive component, the photon transmissive component configured to allow photons to pass through the photon transmissive component. In some embodiments, the third layer of the photonic device includes a charge collection component configured to collect photon-excited charge carriers. In some implementations, the third layer of the optical device includes a waveguide component configured to convey a characteristic of a photon flux incident on at least a portion of the optical device.

According to some embodiments, disclosed herein is an optical device comprising a dielectric transition metal compound phase incorporated on a conductive or semiconducting transition metal compound. In some embodiments, the dielectric transition metal compound phase may include discrete particles. In some embodiments, the dielectric transition metal compound phase may include particles of about 0.1 nm to about 500 nm. In some embodiments, the dielectric transition metal compound phase surrounds the dielectric transition metal compound phase particles.

In some embodiments, the optical device includes a photoactive component. In some embodiments, the photoactive component is configured to absorb radiant energy of photons to generate electrical energy in the circuit. In some embodiments, the photoactive component is configured to generate photons using electrical energy. In some embodiments, the photoactive component comprises a dielectric transition metal compound phase incorporated on a conductive or semiconducting transition metal compound. In some embodiments, the photoactive component comprises a conductive material. In some embodiments, the photoactive component comprises Si, SiGe, Ge, CdTe, GaAs, GaSb and/or InGaAs. In some embodiments, the photoactive component comprises TiF ₃ and TiN.

In some implementations, the optical device includes a photon transmissive component, the photon transmissive component configured to allow photons to pass through the photon transmissive component. In some embodiments, the photon transmissive component comprises a dielectric transition metal compound phase incorporated on a conductive or semiconducting transition metal compound. In some embodiments, the photon transmissive component comprises TiF ₃ and TiN.

In some embodiments, the photonic device includes a charge collection component configured to collect photon-excited charge carriers. In some embodiments, the charge collection component comprises a dielectric transition metal compound phase incorporated on a conductive or semiconducting transition metal compound. In some embodiments, the charge collection component comprises indium tin oxide, doped tin oxide, zinc oxide, doped zinc oxide, conductive polymer, metal grid, carbon nanotube, graphene, or nanowire thin film. In some embodiments, the charge collection component comprises a mixture of TiF ₃ and TiN.

In some implementations, the optical device includes a waveguide component configured to convey a characteristic of a photon flux incident on at least a portion of the optical device. In some embodiments, the waveguide component comprises a dielectric transition metal compound phase incorporated on a conductive or semiconducting transition metal compound.

Example

A number of TiF ₃ films were deposited in a Pulsar® 2000 R&D reactor. The films were deposited by a super-cycle method using a basic super-cycle comprising the following procedure: TiF ₄ sub-cycle and reducing sub-cycle: z[x(TiF ₄ + y(Si ₃ H ₈ + NH ₃ )] and z[x(TiF ₄ + y(Si ₂ H ₆ + NH ₃ )] The reactor temperature was about 370° C.

The basic process parameters are: TiF ₄ ; 3 sec pulse / 5 sec purge, NH ₃ ; 10 sec pulse / 5 sec purge, Si ₂ H ₆ /Si ₃ H ₈ ; 1 second pulse / 5 second purge.

A film was deposited on silicon with native oxide. The film composition was changed by changing the TiF ₄ /reducing sub-cycle ratio (x/y), and the film thickness was controlled by the number of super-cycles (z).

ker D8 Advance를 이용한 x-선 반사도(XRR)로, 두께는 Sentech SE800 타원해석기(ellipsometer)로, 조성은 monochromated AlK_α를 사용하는 PHI Quantum 2000에 의한 x-선 광전자 분광법(분석은 뉴저지, 이스트 윈저에 위치한 EAG 랩이 수행하였음), 및 CuK_α를 사용하는 PANalytical X'Pert Pro MPD X-선 회절기에 의한 x-선 회절(XRD)로 측정하였다. ALD 방법은 놀라운 양의 불화물을 함유한 막들을 생성하였다. XPS 및 XRD 분석으로 이들 막이 TiF₃과 TiN의 혼합물임을 밝혀내었다. 막들은 투명하였고 전기 전도성이었다. 표 1은 상이한 TiF₄/환원성 서브-사이클 비를 갖는 방법들의 조성, 비저항, 거칠기, 밀도 및 성장 속도를 요약한 것이다. The sheet resistance of the films was measured by a four-point probe using CDE Resmap 168, and the thickness, roughness and density were Br

X-ray reflectance (XRR) using a ker D8 Advance, X-ray photoelectron spectroscopy by PHI Quantum 2000 using a Sentech SE800 ellipsometer for thickness and monochromated AlK _α composition (analysis was performed in East Windsor, NJ). was performed by the _EAG Lab located at The ALD method produced films containing surprising amounts of fluoride. XPS and XRD analysis revealed that these films were a mixture of TiF ₃ and TiN. The films were transparent and electrically conductive. Table 1 summarizes the composition, resistivity, roughness, density and growth rate of methods with different TiF ₄ /reducing sub-cycle ratios.

A number of composite films including TiF ₃ particles contained in TiN (TiF ₃ :TiN film) were deposited by the ALD method disclosed herein. These films included TiF ₃ phase particles contained in TiN. The films were deposited by a super-cycle method using a basic super-cycle comprising the following procedure: TiF ₄ sub-cycle with reducing sub-cycle: z[x(TiF4 + y(Si ₂ H ₆ ) + NH ₃ )] and z[x(TiF ₄ + y(Si ₃ H ₈ ) + NH ₃ )]. The reactor temperature was about 370°C.

The basic process parameters are: TiF ₄ ; 3 sec pulse / 5 sec purge, NH ₃ ; 10 sec pulse / 5 sec purge, Si ₂ H ₆ /Si ₃ H ₈ ; 1 second pulse / 5 second purge.

A film was deposited on a silicon substrate with native oxide. The film composition and the size of TiF ₃ phase particles were changed by changing the TiF ₄ /reducing sub-cycle ratio (x/y), and the film thickness was controlled by the number of super-cycles (z). A thin film with TiF ₃ phase particles ranging from 2 nm to 50 nm was deposited.

Bright field and dark field electron microscopy were used to characterize the structure of the thin film. 6 is a brightfield cross-sectional TEM image showing the structure of a TiF ₃ :TiN film deposited on a silicon substrate. 7a and 7b show bright-field and dark-field TEM images of a TiN film including TiF ₃ particles contained therein. The film was deposited by a super-cycle method using a basic super-cycle comprising the following procedure: TiF4 sub-cycle with reducing sub-cycle: z[x(TiF ₄ + y(Si ₂ H ₆ ) + NH ₃ )]. TiF ₃ particles contained in TiN and surrounded by TiN can be seen as black dots in the bright field TEM image of FIG. 7A . TiF ₃ particles contained in TiN and surrounded by TiN can be seen as white dots in the dark field TEM image of FIG. 7B . The size of TiF ₃ particles in this sample ranged from 4.6 nm to 14.8 nm. The sheet resistance of the membrane was characterized by a four-point probe measurement and found to be 263 Ω/sq.

The composition of the thin film was characterized using energy dispersive X-ray spectroscopy (EDS) performed using transmission electron microscopy (TEM). 8 shows a TEM/EDS cross-sectional image of element distributions in a sample TiN film deposited using TiF ₃ particles included therein, TiF ₄ , Si ₂ H ₆ as a reducing agent, and NH ₃ as a nitrogen reactant. These images confirmed the existence of relatively discrete TiF ₃ crystals contained within the TiN matrix.

XPS analysis was performed on the sample film, which showed that the TiF ₃ :TiN thin film had a higher fluoride content near its surface. FIG. 9 shows the XPS depth profile of a sample TiN film deposited using TiF ₃ particles included therein, TiF ₄ , Si ₂ H ₆ as a reducing agent, and NH ₃ as a nitrogen reactant.

Thin films were also deposited by a super-cycle method using a basic super-cycle comprising the following procedure: TiF4 sub-cycle with reducing sub-cycle: z[x(TiF ₄ + y(Si ₂ H ₈ ) + NH ₃ )]. Bright-field and dark-field electron microscopy were used to characterize the structure of the thin film. 10A is a dark field TEM image of a TiN film including TiF ₃ particles contained therein. TiF ₃ particles contained in TiN and surrounded by TiN can be seen as white dots and have a size range of 15.1 nm to 48 nm. Figure 10b shows a cross-sectional dark field image of the sample film. This image shows the dimensions of individual TiF3 particles in the sample film. The sheet resistance of the membrane was also characterized by a four-point probe measurement and found to be 141 Ω/sq.

The composition of the thin film was characterized using energy dispersive X-ray spectroscopy (EDS) performed using transmission electron microscopy (TEM). 11 shows a TEM/EDS cross-sectional image of element distributions in a sample TiN film deposited using TiF ₃ particles included therein, TiF ₄ , Si ₂ H ₈ as a reducing agent, and NH ₃ as a nitrogen reactant. These images confirmed the presence of relatively discrete TiF3 crystals contained within the TiN matrix.

XRD analysis was performed on the sample film, and separate TiF3 and TiN crystallographic phases were identified in the film. 12 shows an XRD pattern of a sample TiN film deposited using TiF ₃ particles included therein, TiF ₄ , Si ₃ H ₈ as a reducing agent, and NH ₃ as a nitrogen reactant.

XPS analysis was performed on the sample film and this analysis showed that the TiF3:TiN thin film had a higher nitrogen content near the silicon substrate interface. 13 shows the XPS depth profile of a sample TiN film deposited using TiF ₃ particles contained therein, TiF ₄ , Si ₃ H ₈ as a reducing agent, and NH ₃ as a nitrogen reactant.

A 30 nm thick sample TiF ₃ :TiN film was deposited on silicon wafers by a super-cycle method using a basic super-cycle comprising the following procedure: TiF4 sub-cycle with reducing sub-cycle: z[ x(TiF ₄ + y(Si ₂ H ₆ ) + NH ₃ )] and z[x(TiF ₄ + y(Si ₃ H ₈ + NH ₃ )] The reactor temperature was 370° C. Fluke 189 voltmeter electrodes spaced a few centimeters apart were brought into contact with the membrane surface and the membrane surface was contacted. The photoactivity was analyzed.Then, a red laser pointer was irradiated toward the surface of the film to generate an illumination spot. FIGS. 14a and 14b show the schematic diagram of this photovoltaic analysis.The electrode closer to the laser pointer illumination spot is It was found that a negative charge was obtained.The potential difference between the electrodes varied from a few millivolts to about 100 millivolts depending on the position of the illumination spot. Figures 14a and 14b show the polarity of the voltmeter electrodes according to the position of the illumination spot on the film. shows the change in

Photoelectric cell samples were prepared using TiF ₃ :TiN thin films by a super-cycle method using a basic super-cycle including the following process: TiF4 sub-cycle with reducing sub-cycle: z[x( TiF ₄ + y(Si ₂ H ₆ + NH ₃ )] and z[x(TiF ₄ + y(Si ₃ H ₈ + NH ₃ )] Fig. 15a shows 20 positioned between a 45 nm thick TiN bottom electrode and a 40 nm thick TiF3:TiN top electrode. Shown is a schematic diagram of a photovoltaic cell comprising p ⁺ -type silicon with thermal oxide top and bottom layers with a thickness of nm.The cell has a surface area of about 4 cm ^2. The cell is exposed to normal office lighting, resulting in 50 An open circuit voltage of mV to 150 mV was produced When exposed to normal office lighting, the cell produced about 2.5 kA into a 120 Ω resistor.

15B shows a schematic diagram of a photovoltaic cell comprising p ⁺ -type silicon with native oxide top and bottom layers positioned between a 45 nm thick TiN bottom electrode and a 60 nm thick TiF3:TiN top electrode. Again, the cell had a surface area of about 4 cm ² . Cells were irradiated with halogen lamp illumination (Osram 50 W, 240 V bulb, 2800K), which produced an open circuit voltage of about 100 mV to 450 mV as measured with a Fluke 189 voltmeter.

While specific embodiments and examples have been disclosed below, it will be understood by those skilled in the art that the scope of the claims extends beyond the specifically disclosed embodiments to alternative embodiments and/or uses of the present invention and obvious modifications and equivalents thereof.

Claims (38)

A device comprising a layer comprising a dielectric transition metal compound phase contained on a conductive or semiconducting transition metal compound, wherein the dielectric transition metal compound phase comprises TiF ₃ and the conductive or semiconducting transition metal compound phase comprises TiN little boy. The device of claim 1 , wherein the device is a photonic device. The optical device according to claim 2, wherein the dielectric transition metal compound phase is composed of particles having a diameter of 0.1 nm to 500 nm. The optical device of claim 2 , wherein the conductive or semiconducting transition metal compound phase surrounds discrete dielectric transition metal compound phase particles. 3. The method of claim 2, wherein the layer comprises a photoactive material,
and the layer absorbs radiant energy of photons incident on the surface of the optical device to produce electrical energy in an electrical circuit. The photonic device of claim 2 , wherein the layer uses electrical energy in an electrical circuit to produce photons. 3. The method of claim 2, wherein said layer comprising said dielectric transition metal compound phase comprised on said conductive or semiconducting transition metal compound acts as a photon transmissive layer;
The photon transmissive layer is an optical device, such that photons incident on the surface of the photon transmissive layer pass through the photon transmissive layer to the photoactive layer. The optical device of claim 2 , wherein the layer comprising a dielectric transition metal compound phase included on the conductive or semiconducting transition metal compound acts as a charge collection component that collects photon-excited charge carriers. 3. The optical device of claim 2, wherein the layer comprising a dielectric transition metal compound phase included on the conductive or semiconducting transition metal compound directs photon flux incident on the first portion of the optical device to a second portion of the optical device. An optical device that acts as a transmissible waveguide component. 3. The method of claim 2, further comprising a charge collection component that collects photon excited charge carriers, the charge collection component comprising: indium tin oxide, doped tin oxide, zinc oxide, doped zinc oxide, a conductive polymer; An optical device comprising at least one of a metal grid, carbon nanotubes, graphenes, or a nanowire thin film. The optical device of claim 2 , further comprising a photoactive component comprising at least one of Si, SiGe, Ge, CdTe, GaAs, GaSb, InGaAs. A photoactive material comprising a dielectric transition metal compound phase comprised on a conductive or semiconducting transition metal compound, wherein the dielectric transition metal compound phase comprises TiF ₃ and the transition metal compound phase comprises TiN. The photoactive material of claim 12 , wherein the photoactive material absorbs the radiant energy of photons to produce electrical energy in an electrical circuit. The photoactive material of claim 12 , wherein the photoactive material is an electrically conductive material that transmits photons. 13. The method of claim 12, wherein the photoactive material is a waveguide material,
wherein the waveguide material is capable of transmitting a photon flux incident on a first portion of the waveguide material to a second portion of the waveguide material. A vapor deposition method for depositing a layer in an optical device comprising:
The layer comprises a dielectric transition metal compound phase included in a conductive or semiconducting transition metal compound phase, wherein the dielectric transition metal compound phase comprises TiF ₃ and the conductive or semiconducting transition metal compound phase comprises TiN. which is a vapor deposition method. 17. The method of claim 16, wherein the vapor deposition method comprises a plurality of super-cycles, each super-cycle comprising a dielectric transition metal compound sub-cycle and a reducing sub-cycle;
the dielectric transition metal compound sub-cycle comprises contacting a substrate with a vapor phase dielectric transition metal compound; and
wherein the reducing sub-cycle comprises contacting the substrate alternately and sequentially with a reducing agent and a nitrogen reactant. 18. The method of claim 17, wherein the reducing agent comprises silane or borane. 18. The method of claim 17, wherein the nitrogen reactant comprises at least one of ammonia, N ₂ H ₄ , nitrogen atoms, a nitrogen containing plasma, and nitrogen radicals. A method for forming a layer in an optical device, comprising:
depositing the layer comprising a dielectric transition metal compound phase comprised on a conductive or semiconducting transition metal compound on a substrate for the optical device by a vapor deposition method;
The dielectric transition metal compound phase comprises TiF ₃ , and
wherein the layer is part of the optical device. 21. The method of claim 20, wherein the layer comprises 0.1 to 10 at% silicon. 21. The method of claim 20, wherein the layer comprises 5 to 50 atomic percent nitrogen. 21. The method of claim 20, wherein the layer has a resistivity of 5Х10 ³ μΩcm to 5Х10 ⁶ μΩcm. The method of claim 20 , wherein the layer has a thickness of less than 3 nm. 21. The method of claim 20, wherein the vapor deposition method may comprise a plurality of super-cycles, each super-cycle comprising a dielectric transition metal compound sub-cycle and a reducing sub-cycle,
the dielectric transition metal compound sub-cycle comprises contacting the substrate with a vapor phase dielectric transition metal compound; and
wherein the reducing sub-cycle comprises contacting the substrate with a reducing agent and a nitrogen reactant alternately and sequentially. 26. The method of claim 25, wherein the dielectric transition metal compound comprises Ti. 26. The method of claim 25, wherein the dielectric transition metal compound is a metal fluoride. 26. The method of claim 25, wherein the dielectric transition metal compound is TiF ₄ . 26. The method of claim 25, wherein the reducing agent comprises at least one of silane, disilane, trisilane, borane, diborane, and triborane. The method of claim 25 , wherein the reducing agent is Si ₃ H ₈ . The method of claim 25 , wherein the nitrogen reactant comprises at least one of ammonia, N ₂ H ₄ , nitrogen atoms, a nitrogen containing plasma, and nitrogen radicals. The method of claim 25 , wherein the dielectric transition metal compound sub-cycle and the reducing sub-cycle are performed in a ratio of 0.1 to 1 in at least one of the plurality of super-cycles. The method of claim 20 , wherein the conductive or semiconducting transition metal compound phase comprises a transition metal element, a transition metal alloy, a transition metal oxide, a transition metal nitride, a transition metal silicide, or a transition metal carbide. The method of claim 20 , wherein the conductive or semiconducting transition metal compound phase comprises TiN. The method of claim 20 , wherein the dielectric transition metal compound phase consists of particles having a diameter between 0.1 nm and 500 nm. 21. The method of claim 20, wherein the conductive or semiconducting transition metal compound phase surrounds discrete dielectric transition metal compound phase particles in the layer. The method of claim 20 , wherein the layer comprising a dielectric transition metal compound phase incorporated on a conductive or semiconducting transition metal compound acts as a photon transmissive layer in the optical device. The method of claim 20 , wherein the layer comprising a dielectric transition metal compound phase incorporated on a conductive or semiconducting transition metal compound acts as a charge collection component or a waveguide component in the optical device.

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